High-Purity Dibasic Acid Compositions and Methods of Making the Same

ABSTRACT

High-purity dibasic acid compositions are generally disclosed. In some embodiments, the dibasic acid compositions are solutions or suspensions. In some other embodiments, the compositions are solid-state compositions. In some such embodiments, the solid-state compositions include a dibasic acid as a crystalline solid and further include a low quantity of certain impurities, such as monobasic acids, various esters, and the like. Methods and systems for making such high-purity dibasic acid compositions are also disclosed.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation application of U.S. patentapplication Ser. No. 15/287,986, filed Oct. 7, 2016, which is acontinuation of U.S. patent application Ser. No. 14/502,382, filed Sep.30, 2014, which claims the benefit of priority of U.S. ProvisionalApplication No. 61/888,440, filed Oct. 8, 2013. The contents of each ofthe foregoing applications are hereby incorporated by reference asthough set forth herein in their entirety.

TECHNICAL FIELD

High-purity dibasic acid compositions are generally disclosed. In someembodiments, the dibasic acid compositions are solutions or suspensions.In some other embodiments, the compositions are solid-statecompositions. In some such embodiments, the solid-state compositionscomprise a dibasic acid as a crystalline solid and further comprise alow quantity of certain impurities, such as monobasic acids, variousesters, and the like. Methods and systems for making such high-puritydibasic acid compositions are also disclosed.

BACKGROUND

Dibasic acids are organic compounds having two carboxylic acid groups.Such compounds can be used in a wide array of different ways. Because oftheir difunctionality, they are commonly used in making certainpolymers. For example, a polyamide can be made by reacting a dibasicacid with a diamine, i.e., an organic compound having two amine groups.As another example, a polyester can be made by reacting a dibasic acidwith a diol, i.e., an organic compound having two hydroxyl groups.

In certain instances, it may be desirable to use dibasic acids in ahighly pure form, as the presence of impurities may cause certainundesirable events to occur. For example, if a dibasic acid compositioncontains a substantial amount of monobasic acid impurity, it can causeearly chain termination in the polymerization process, thereby resultingin polymer chains that may have a lower molecular weight than desired.

Thus, there is a continuing need to develop cost-effective and scalablemethods of making dibasic acids that result in high-purity compositions,especially compositions that have a low concentration of monobasic acidimpurity.

SUMMARY

In a first aspect, the disclosure provides methods for hydrolyzing adibasic ester, including: introducing a dibasic ester to a reactor; andreacting the dibasic ester with water in the reactor at an elevatedtemperature to form a dibasic acid and an alcohol; wherein at least aportion of the formed alcohol is removed from the reactor during thereacting step.

In a second aspect, the disclosure provides methods of hydrolyzing adibasic ester, including: introducing a first composition to a reactor,the first composition comprising at least 50 grams of dibasic ester; andreacting the dibasic ester in the reactor with water to form a secondcomposition comprising a dibasic acid; wherein the second composition issubstantially free of colored impurities.

In a third aspect, the disclosure provides hydrolysis reactors,including: a pressurizable vessel disposed proximate to a heat source,wherein the pressurizable vessel comprises an inlet and a an outlet; awater source, wherein the water source is in fluid communication withthe liquid inlet of the pressurizable vessel; and a condenser, whereinthe condenser is in fluid communication with the gas outlet of thepressurizable vessel via an adjustable pressure regulator disposedbetween the condenser and the gas outlet.

In a fourth aspect, the disclosure provides methods of forming apurified solid-state dibasic acid composition, including: providing afirst composition, which comprises a first amount of dibasic acid and afirst amount of one or more monobasic acids, each dissolved in a solventsystem; and cooling the first composition to form a second composition,which comprises a second amount the dibasic acid in solid-state formsuspended in the solvent system, and a second amount of the one or moremonobasic acids dissolved in the solvent system.

In a fifth aspect, the disclosure provides methods of forming a dibasicacid, including: reacting a first olefin ester and an second olefinester in the presence of a metathesis catalyst to form a first alkeneand an unsaturated dibasic ester; hydrogenating the unsaturated dibasicester to form a saturated dibasic ester; and converting the saturateddibasic ester to a saturated dibasic acid. In some embodiments, thefirst olefin ester and the second olefin ester are the same compound. Insome other embodiments, the first olefin ester and the second olefinester are different compounds. In some such embodiments, the firstolefin ester is a terminal olefin ester and the second olefin ester isan internal olefin ester.

Further aspects and embodiments are provided in the foregoing drawings,detailed description and claims.

BRIEF DESCRIPTION OF THE DRAWINGS

The following drawings are provided to illustrate certain embodimentsdescribed herein. The drawings are merely illustrative, and are notintended to limit the scope of claimed inventions and are not intendedto show every potential feature or embodiment of the claimed inventions.The drawings are not necessarily drawn to scale; in some instances,certain elements of the drawing may be enlarged with respect to otherelements of the drawing for purposes of illustration.

FIG. 1 shows an illustrative embodiment of a method for hydrolyzing adibasic ester to a dibasic acid.

FIG. 2 shows an illustrative embodiment of a reactor suitable forhydrolyzing a dibasic ester to a dibasic acid.

FIG. 3 shows an illustrative embodiments for forming a purifiedsolid-state dibasic acid composition.

FIG. 4 shows an illustrative embodiment for forming a dibasic acid.

FIG. 5 shows an illustrative embodiment for forming a dibasic acid.

FIG. 6 shows an illustrative embodiment for forming a dibasic acid.

FIG. 7 shows an illustrative embodiment for forming a dibasic acid.

FIG. 8 shows an illustrative embodiment for forming a dibasic acid.

FIG. 9 shows an illustrative embodiment for making an unsaturateddibasic ester from a feedstock comprising a natural oil.

FIG. 10 shows an illustrative embodiment for making an unsaturateddibasic ester from a feedstock comprising a natural oil.

DETAILED DESCRIPTION

The following description recites various aspects and embodiments of theinventions disclosed herein. No particular embodiment is intended todefine the scope of the invention. Rather, the embodiments providenon-limiting examples of various compositions, and methods that areincluded within the scope of the claimed inventions. The description isto be read from the perspective of one of ordinary skill in the art.Therefore, information that is well known to the ordinarily skilledartisan is not necessarily included.

Definitions

The following terms and phrases have the meanings indicated below,unless otherwise provided herein. This disclosure may employ other termsand phrases not expressly defined herein. Such other terms and phrasesshall have the meanings that they would possess within the context ofthis disclosure to those of ordinary skill in the art. In someinstances, a term or phrase may be defined in the singular or plural. Insuch instances, it is understood that any term in the singular mayinclude its plural counterpart and vice versa, unless expresslyindicated to the contrary.

As used herein, the singular forms “a,” “an,” and “the” include pluralreferents unless the context clearly dictates otherwise. For example,reference to “a substituent” encompasses a single substituent as well astwo or more substituents, and the like.

As used herein, “for example,” “for instance,” “such as,” or “including”are meant to introduce examples that further clarify more generalsubject matter. Unless otherwise expressly indicated, such examples areprovided only as an aid for understanding embodiments illustrated in thepresent disclosure, and are not meant to be limiting in any fashion. Nordo these phrases indicate any kind of preference for the disclosedembodiment.

As used herein, “natural oil,” “natural feedstock,” or “natural oilfeedstock” refer to oils derived from plants or animal sources. Theseterms include natural oil derivatives, unless otherwise indicated. Theterms also include modified plant or animal sources (e.g., geneticallymodified plant or animal sources), unless indicated otherwise. Examplesof natural oils include, but are not limited to, vegetable oils, algaeoils, fish oils, animal fats, tall oils, derivatives of these oils,combinations of any of these oils, and the like. Representativenon-limiting examples of vegetable oils include rapeseed oil (canolaoil), coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanutoil, safflower oil, sesame oil, soybean oil, sunflower oil, linseed oil,palm kernel oil, tung oil, jatropha oil, mustard seed oil, pennycressoil, camelina oil, hempseed oil, and castor oil. Representativenon-limiting examples of animal fats include lard, tallow, poultry fat,yellow grease, and fish oil. Tall oils are by-products of wood pulpmanufacture. In some embodiments, the natural oil or natural oilfeedstock comprises one or more unsaturated glycerides (e.g.,unsaturated triglycerides). In some such embodiments, the natural oilfeedstock comprises at least 50% by weight, or at least 60% by weight,or at least 70% by weight, or at least 80% by weight, or at least 90% byweight, or at least 95% by weight, or at least 97% by weight, or atleast 99% by weight of one or more unsaturated triglycerides, based onthe total weight of the natural oil feedstock.

As used herein, “natural oil derivatives” refers to the compounds ormixtures of compounds derived from a natural oil using any one orcombination of methods known in the art. Such methods include but arenot limited to saponification, fat splitting, transesterification,esterification, hydrogenation (partial, selective, or full),isomerization, oxidation, and reduction. Representative non-limitingexamples of natural oil derivatives include gums, phospholipids,soapstock, acidulated soapstock, distillate or distillate sludge, fattyacids and fatty acid alkyl ester (e.g. non-limiting examples such as2-ethylhexyl ester), hydroxy substituted variations thereof of thenatural oil. For example, the natural oil derivative may be a fatty acidmethyl ester (“FAME”) derived from the glyceride of the natural oil. Insome embodiments, a feedstock includes canola or soybean oil, as anon-limiting example, refined, bleached, and deodorized soybean oil(i.e., RBD soybean oil). Soybean oil typically comprises about 95%weight or greater (e.g., 99% weight or greater) triglycerides of fattyacids. Major fatty acids in the polyol esters of soybean oil includesaturated fatty acids, as a non-limiting example, palmitic acid(hexadecanoic acid) and stearic acid (octadecanoic acid), andunsaturated fatty acids, as a non-limiting example, oleic acid(9-octadecenoic acid), linoleic acid (9, 12-octadecadienoic acid), andlinolenic acid (9,12,15-octadecatrienoic acid).

As used herein, “metathesis catalyst” includes any catalyst or catalystsystem that catalyzes an olefin metathesis reaction.

As used herein, “metathesize” or “metathesizing” refer to the reactingof a feedstock in the presence of a metathesis catalyst to form a“metathesized product” comprising new olefinic compounds, i.e.,“metathesized” compounds. Metathesizing is not limited to any particulartype of olefin metathesis, and may refer to cross-metathesis (i.e.,co-metathesis), self-metathesis, ring-opening metathesis, ring-openingmetathesis polymerizations (“ROMP”), ring-closing metathesis (“RCM”),and acyclic diene metathesis (“ADMET”). In some embodiments,metathesizing refers to reacting two triglycerides present in a naturalfeedstock (self-metathesis) in the presence of a metathesis catalyst,wherein each triglyceride has an unsaturated carbon-carbon double bond,thereby forming a new mixture of olefins and esters which may include atriglyceride dimer. Such triglyceride dimers may have more than oneolefinic bond, thus higher oligomers also may form. Additionally, insome other embodiments, metathesizing may refer to reacting an olefin,such as ethylene, and a triglyceride in a natural feedstock having atleast one unsaturated carbon-carbon double bond, thereby forming newolefinic molecules as well as new ester molecules (cross-metathesis).

As used herein, “hydrocarbon” refers to an organic group composed ofcarbon and hydrogen, which can be saturated or unsaturated, and caninclude aromatic groups. The term “hydrocarbyl” refers to a monovalentor polyvalent hydrocarbon moiety.

As used herein, “olefin” or “olefins” refer to compounds having at leastone unsaturated carbon-carbon double bond. In certain embodiments, theterm “olefins” refers to a group of unsaturated carbon-carbon doublebond compounds with different carbon lengths. Unless noted otherwise,the terms “olefin” or “olefins” encompasses “polyunsaturated olefins” or“poly-olefins,” which have more than one carbon-carbon double bond. Asused herein, the term “monounsaturated olefins” or “mono-olefins” refersto compounds having only one carbon-carbon double bond. A compoundhaving a terminal carbon-carbon double bond can be referred to as a“terminal olefin,” while an olefin having a non-terminal carbon-carbondouble bond can be referred to as an “internal olefin.”

As used herein, the term “low-molecular-weight olefin” may refer to anyone or combination of unsaturated straight, branched, or cyclichydrocarbons in the C₂₋₁₄ range. Low-molecular-weight olefins include“alpha-olefins” or “terminal olefins,” wherein the unsaturatedcarbon-carbon bond is present at one end of the compound.Low-molecular-weight olefins may also include diener or trienes.Low-molecular-weight olefins may also include internal olefins or“low-molecular-weight internal olefins.” In certain embodiments, thelow-molecular-weight internal olefin is in the C₄₋₁₄ range. Examples oflow-molecular-weight olefins in the C₂₋₆ range include, but are notlimited to: ethylene, propylene, 1-butene, 2-butene, isobutene,1-pentene, 2-pentene, 3-pentene, 2-methyl-1-butene, 2-methyl-2-butene,3-methyl-1-butene, cyclopentene, 1,4-pentadiene, 1-hexene, 2-hexene,3-hexene, 4-hexene, 2-methyl-1-pentene, 3-methyl-1-pentene,4-methyl-1-pentene, 2-methyl-2-pentene, 3-methyl-2-pentene,4-methyl-2-pentene, 2-methyl-3-pentene, and cyclohexene. Non-limitingexamples of low-molecular-weight olefins in the C₇₋₉ range include1,4-heptadiene, 1-heptene, 3,6-nonadiene, 3-nonene, 1,4,7-octatriene.Other possible low-molecular-weight olefins include styrene and vinylcyclohexane. In certain embodiments, it is preferable to use a mixtureof olefins, the mixture comprising linear and branchedlow-molecular-weight olefins in the C₄₋₁₀ range. In one embodiment, itmay be preferable to use a mixture of linear and branched C₄ olefins(i.e., combinations of: 1-butene, 2-butene, and/or isobutene). In otherembodiments, a higher range of C_(11-C14) may be used.

In some instances, the olefin can be an “alkene,” which refers to astraight- or branched-chain non-aromatic hydrocarbon having 2 to 30carbon atoms and one or more carbon-carbon double bonds, which may beoptionally substituted, as herein further described, with multipledegrees of substitution being allowed. A “monounsaturated alkene” refersto an alkene having one carbon-carbon double bond, while a“polyunsaturated alkene” refers to an alkene having two or morecarbon-carbon double bonds. A “lower alkene,” as used herein, refers toan alkene having from 2 to 10 carbon atoms.

As used herein, “alpha-olefin” refers to an olefin (as defined above)that has a terminal carbon-carbon double bond. In some embodiments, thealpha-olefin is a terminal alkene, which is an alkene (as defined above)having a terminal carbon-carbon double bond. Additional carbon-carbondouble bonds can be present.

As used herein, “ester” or “esters” refer to compounds having thegeneral formula: R—COO—R′, wherein R and R′ denote any organic group(such as alkyl, aryl, or silyl groups) including those bearingheteroatom-containing substituent groups. In certain embodiments, R andR′ denote alkyl, alkenyl, aryl, or alcohol groups. In certainembodiments, the term “esters” may refer to a group of compounds withthe general formula described above, wherein the compounds havedifferent carbon lengths. In certain embodiments, the esters may beesters of glycerol, which is a trihydric alcohol. The term “glyceride”can refer to esters where one, two, or three of the —OH groups of theglycerol have been esterified. Thus, the term “unsaturated glyceride”can refer to monoglycerides, diglycerides, or triglycerides, where oneor more of the acid portions of the ester contain unsaturation, e.g., acarbon-carbon double bond.

It is noted that an olefin may also comprise an ester, and an ester mayalso comprise an olefin, if the R or R′ group in the general formulaR—COO—R′ contains an unsaturated carbon-carbon double bond. Suchcompounds can be referred to as “olefin esters.” Further, a “terminalolefin ester” may refer to an ester compound where R has an olefinpositioned at the end of the chain. An “internal olefin ester” may referto an ester compound where R has an olefin positioned at an internallocation on the chain. Additionally, the term “terminal olefin” mayrefer to an ester or an acid thereof where R′ denotes hydrogen or anyorganic compound (such as an alkyl, aryl, or silyl group) and R has anolefin positioned at the end of the chain, and the term “internalolefin” may refer to an ester or an acid thereof where R′ denoteshydrogen or any organic compound (such as an alkyl, aryl, or silylgroup) and R has an olefin positioned at an internal location on thechain.

As used herein, “acid” or “acids” refer to compounds having the generalformula: R—COOH, wherein R denotes any organic moiety (such as alkyl,aryl, or silyl groups), including those bearing heteroatom-containingsubstituent groups. In certain embodiments, R denotes alkyl, alkenyl,aryl, or alcohol groups. In certain embodiments, the term “acids” mayrefer to a group of compounds with the general formula described above,wherein the compounds have different carbon lengths. The term “carboxyl”refers to a —COOH moiety. The term “carboxylated” refers to a “carboxyl”group formed on another group or compound.

As used herein, the term “dibasic ester” may refer to compounds havingthe general formula R—OOC—Y—COO—R′, wherein Y, R, and R′ denote anyorganic compound (such as alkyl, aryl, or silyl groups), including thosebearing heteroatom containing substituent groups. In certainembodiments, Y is a saturated or unsaturated hydrocarbon, and R and R′are alkyl or alkenyl groups. In instances where Y is a saturatedhydrocarbon, the dibasic ester can be referred to as a “saturateddibasic ester.” In instances where Y is an unsaturated hydrocarbon, thedibasic ester can be referred to as an “unsaturated dibasic ester.”

As used herein, the term “dibasic acid” may refer to compounds havingthe general formula R—OOC—Y—COO—R′, wherein R and R′ are hydrogen atoms,and Y denotes any organic compound (such as an alkyl, aryl, or silylgroup), including those bearing heteroatom substituent groups. Incertain embodiments, Y is a saturated or unsaturated hydrocarbon. Ininstances where Y is a saturated hydrocarbon, the dibasic acid can bereferred to as a “saturated dibasic acid.” In instances where Y is anunsaturated hydrocarbon, the dibasic acid can be referred to as an“unsaturated dibasic acid.”

As used herein, “alcohol” or “alcohols” refer to compounds having thegeneral formula: R—OH, wherein R denotes any organic moiety (such asalkyl, aryl, or silyl groups), including those bearingheteroatom-containing substituent groups. In certain embodiments, Rdenotes alkyl, alkenyl, aryl, or alcohol groups. In certain embodiments,the term “alcohol” or “alcohols” may refer to a group of compounds withthe general formula described above, wherein the compounds havedifferent carbon lengths. The term “hydroxyl” refers to a —OH moiety.

As used herein, “amine” or “amines” refer to compounds having thegeneral formula: R—N(R′)(R″), wherein R, R′, and R″ denote a hydrogen oran organic moiety (such as alkyl, aryl, or silyl groups), includingthose bearing heteroatom-containing substituent groups. In certainembodiments, R, R′, and R″ denote a hydrogen or an alkyl, alkenyl, aryl,or alcohol groups. In certain embodiments, the term “amines” may referto a group of compounds with the general formula described above,wherein the compounds have different carbon lengths. The term “amino”refers to a —N(R)(R′) moiety.

As used herein, “alkyl” refers to a straight or branched chain saturatedhydrocarbon having 1 to 30 carbon atoms, which may be optionallysubstituted, as herein further described, with multiple degrees ofsubstitution being allowed. Examples of “alkyl,” as used herein,include, but are not limited to, methyl, ethyl, n-propyl, isopropyl,isobutyl, n-butyl, sec-butyl, tert-butyl, isopentyl, n-pentyl,neopentyl, n-hexyl, and 2-ethylhexyl. The number of carbon atoms in analkyl group is represented by the phrase “C_(x-y) alkyl,” which refersto an alkyl group, as herein defined, containing from x toy, inclusive,carbon atoms. Thus, “C₁₋₆alkyl” represents an alkyl chain having from 1to 6 carbon atoms and, for example, includes, but is not limited to,methyl, ethyl, n-propyl, isopropyl, isobutyl, n-butyl, sec-butyl,tert-butyl, isopentyl, n-pentyl, neopentyl, and n-hexyl. In someinstances, the “alkyl” group can be divalent, in which case the groupcan alternatively be referred to as an “alkylene” group. Also, in someinstances, one or more of the carbon atoms in the alkyl or alkylenegroup can be replaced by a heteroatom (e.g., selected from nitrogen,oxygen, or sulfur, including N-oxides, sulfur oxides, and sulfurdioxides, where feasible), and is referred to as a “heteroalkyl” or“heteroalkylene” group, respectively. Non-limiting examples include“oxyalkyl” or “oxyalkylene” groups, which are groups of the followingformulas: -[-(alkylene)-O-]_(x)-alkyl, or-[-(alkylene)-O-]_(x)-alkylene-, respectively, where x is 1 or more,such as 1, 2, 3, 4, 5, 6, 7, or 8.

As used herein, “alkenyl” refers to a straight or branched chainnon-aromatic hydrocarbon having 2 to 30 carbon atoms and having one ormore carbon-carbon double bonds, which may be optionally substituted, asherein further described, with multiple degrees of substitution beingallowed. Examples of “alkenyl,” as used herein, include, but are notlimited to, ethenyl, 2-propenyl, 2-butenyl, and 3-butenyl. The number ofcarbon atoms in an alkenyl group is represented by the phrase “C_(x-y)alkenyl,” which refers to an alkenyl group, as herein defined,containing from x to y, inclusive, carbon atoms. Thus, “C₂₋₆ alkenyl”represents an alkenyl chain having from 2 to 6 carbon atoms and, forexample, includes, but is not limited to, ethenyl, 2-propenyl,2-butenyl, and 3-butenyl. In some instances, the “alkenyl” group can bedivalent, in which case the group can alternatively be referred to as an“alkenylene” group. Also, in some instances, one or more of thesaturated carbon atoms in the alkenyl or alkenylene group can bereplaced by a heteroatom (e.g., selected from nitrogen, oxygen, orsulfur, including N-oxides, sulfur oxides, and sulfur dioxides, wherefeasible), and is referred to as a “heteroalkenyl” or “heteroalkenylene”group, respectively.

As used herein, “alkynyl” refers to a straight or branched chainnon-aromatic hydrocarbon having 2 to 30 carbon atoms and having one ormore carbon-carbon triple bonds, which may be optionally substituted, asherein further described, with multiple degrees of substitution beingallowed. Examples of “alkynyl,” as used herein, include, but are notlimited to, ethynyl, 2-propynyl, 2-butynyl, and 3-butynyl. The number ofcarbon atoms in an alkynyl group is represented by the phrase “C_(x-y)alkynyl,” which refers to an alkynyl group, as herein defined,containing from x toy, inclusive, carbon atoms. Thus, “C₂₋₆alkynyl”represents an alkynyl chain having from 2 to 6 carbon atoms and, forexample, includes, but is not limited to, ethynyl, 2-propynyl,2-butynyl, and 3-butynyl. In some instances, the “alkynyl” group can bedivalent, in which case the group can alternatively be referred to as an“alkynylene” group. Also, in some instances, one or more of thesaturated carbon atoms in the alkynyl group can be replaced by aheteroatom (e.g., selected from nitrogen, oxygen, or sulfur, includingN-oxides, sulfur oxides, and sulfur dioxides, where feasible), and isreferred to as a “heteroalkynyl” group.

As used herein, “cycloalkyl” refers to an aliphatic saturated orunsaturated hydrocarbon ring system having 1 to 20 carbon atoms, whichmay be optionally substituted, as herein further described, withmultiple degrees of substitution being allowed. Examples of“cycloalkyl,” as used herein, include, but are not limited to,cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl,cycloheptyl, cyclooctyl, adamantyl, and the like. The number of carbonatoms in a cycloalkyl group is represented by the phrase “C_(x-y)alkyl,” which refers to a cycloalkyl group, as herein defined,containing from x to y, inclusive, carbon atoms. Thus, “C₃₋₁₀cycloalkyl” represents a cycloalkyl having from 3 to 10 carbon atomsand, for example, includes, but is not limited to, cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, cycloheptyl,cyclooctyl, and adamantyl. In some instances, the “cycloalkyl” group canbe divalent, in which case the group can alternatively be referred to asa “cycloalkylene” group. Also, in some instances, one or more of thecarbon atoms in the cycloalkyl or cycloalkylene group can be replaced bya heteroatom (e.g., selected from nitrogen, oxygen, or sulfur, includingN-oxides, sulfur oxides, and sulfur dioxides, where feasible), and isreferred to as a “heterocycloalkyl” or “heterocycloalkylene” group,respectively.

As used herein, “alkoxy” refers to —OR, where R is an alkyl group (asdefined above). The number of carbon atoms in an alkyl group isrepresented by the phrase “C_(x-y) alkoxy,” which refers to an alkoxygroup having an alkyl group, as herein defined, containing from x to y,inclusive, carbon atoms.

As used herein, “halogen” or “halo” refers to a fluorine, chlorine,bromine, and/or iodine atom. In some embodiments, the terms refer tofluorine and/or chlorine. As used herein, “haloalkyl” or “haloalkoxy”refer to alkyl or alkoxy groups, respectively, substituted by one ormore halogen atoms. The terms “perfluoroalkyl” or “perfluoroalkoxy”refer to alkyl groups and alkoxy groups, respectively, where everyavailable hydrogen is replaced by fluorine.

As used herein, “substituted” refers to substitution of one or morehydrogen atoms of the designated moiety with the named substituent orsubstituents, multiple degrees of substitution being allowed unlessotherwise stated, provided that the substitution results in a stable orchemically feasible compound. A stable compound or chemically feasiblecompound is one in which the chemical structure is not substantiallyaltered when kept at a temperature from about −80° C. to about +40° C.,in the absence of moisture or other chemically reactive conditions, forat least a week, or a compound which maintains its integrity long enoughto be useful for therapeutic or prophylactic administration to apatient. As used herein, the phrases “substituted with one or more . . .” or “substituted one or more times . . . ” refer to a number ofsubstituents that equals from one to the maximum number of substituentspossible based on the number of available bonding sites, provided thatthe above conditions of stability and chemical feasibility are met.

As used herein, “yield” refers to the amount of reaction product formedin a reaction. When expressed with units of percent (%), the term yieldrefers to the amount of reaction product actually formed, as apercentage of the amount of reaction product that would be formed if allof the limiting reactant were converted into the product.

As used herein, “mix” or “mixed” or “mixture” refers broadly to anycombining of two or more compositions. The two or more compositions neednot have the same physical state; thus, solids can be “mixed” withliquids, e.g., to form a slurry, suspension, or solution. Further, theseterms do not require any degree of homogeneity or uniformity ofcomposition. This, such “mixtures” can be homogeneous or heterogeneous,or can be uniform or non-uniform. Further, the terms do not require theuse of any particular equipment to carry out the mixing, such as anindustrial mixer.

As used herein, “optionally” means that the subsequently describedevent(s) may or may not occur. In some embodiments, the optional eventdoes not occur. In some other embodiments, the optional event does occurone or more times.

As used herein, “comprise” or “comprises” or “comprising” or “comprisedof” refer to groups that are open, meaning that the group can includeadditional members in addition to those expressly recited. For example,the phrase, “comprises A” means that A must be present, but that othermembers can be present too. The terms “include,” “have,” and “composedof” and their grammatical variants have the same meaning. In contrast,“consist of” or “consists of” or “consisting of” refer to groups thatare closed. For example, the phrase “consists of A” means that A andonly A is present.

As used herein, “or” is to be given its broadest reasonableinterpretation, and is not to be limited to an either/or construction.Thus, the phrase “comprising A or B” means that A can be present and notB, or that B is present and not A, or that A and B are both present.Further, if A, for example, defines a class that can have multiplemembers, e.g., A₁ and A₂, then one or more members of the class can bepresent concurrently.

As used herein, the various functional groups represented will beunderstood to have a point of attachment at the functional group havingthe hyphen or dash (-) or an asterisk (*). In other words, in the caseof —CH₂CH₂CH₃, it will be understood that the point of attachment is theCH₂ group at the far left. If a group is recited without an asterisk ora dash, then the attachment point is indicated by the plain and ordinarymeaning of the recited group.

As used herein, multi-atom bivalent species are to be read from left toright. For example, if the specification or claims recite A-D-E and D isdefined as —OC(O)—, the resulting group with D replaced is: A-OC(O)-Eand not A-C(O)O-E.

Other terms are defined in other portions of this description, eventhough not included in this subsection.

Hydrolysis of Dibasic Esters

In certain aspects, the disclosure provides methods for hydrolyzing adibasic ester, comprising: introducing a dibasic ester to a reactor; andreacting the dibasic ester with water in the reactor to form a dibasicacid and an alcohol.

The methods include introducing a dibasic ester to a reactor. The acidcan be introduced in any suitable manner. For example, in someembodiments, the dibasic ester is added to the reactor, either alone orwith other ingredients. In some other embodiments, however, the dibasicacid is generated in the reactor, for example, as the product of achemical reaction that occurs in the reactor. The dibasic ester can bein any suitable form, for example, as a solid, in a slurry with asuitable liquid carrier, in a suspension with a suitable liquid carrier,or dissolved in a solvent. In some embodiments, the dibasic acid isintroduced to the reactor as a solid composition. In some otherembodiments, the dibasic ester is introduced to the reactor dissolved ina solution. Any suitable solvent system can be used for the solution,including, but not limited to, solvent systems that include ethylacetate, acetonitrile, heptane, hexane, diethyl ether, methyl tert-butylether (MBTE), petroleum ether, toluene, ortho-xylene, meta-xylene,para-xylene, acetone, dimethylformamide, tetrahydrofuran, methylenedichloride, 1-butanol, isopropyl alcohol, isopropyl acetate,1,2-dimethoxyethane, and dimethyl sulfoxide. In some embodiments, thesolvent system comprises toluene. In some embodiments, these solventsystems can include compounds that are miscible with water. In someembodiments, these solvent systems can include compounds that are notmiscible with water. In some embodiments, these solvent systems caninclude one or more compounds that are not miscible with water and oneor more compounds that are miscible in water.

In some embodiments, the composition can also include other organicesters, such as monobasic esters, but in smaller relative quantitiesthan the dibasic ester. In some embodiments, these monobasic esters caninclude esters of various saturated fatty acids. These include, but arenot limited to, esters of hexanoic acid, heptanoic acid, octanoic acid,nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid,tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoicacid, heptadecanoic acid, octadecanoic acid, and the like. In someembodiments, these monobasic esters can include esters of variousunsaturated fatty acids, such as esters of octenoic acid, nonenoic acid,decenoic acid, undecenoic acid, dodecenoic acid, tridecenoic acid,tetradecenoic acid, pentadecenoic acid, hexadecenoic acid, heptadecenoicacid, octadecenoic acid, tridecadienoic acid, hexadecadienoic acid, andthe like. In some embodiments, such esters are esters of simplealiphatic alcohols, such as methyl esters, ethyl esters, or isopropylesters, of any of the aforementioned acids.

In some embodiments, the dibasic ester can be formed by a process thatincludes self-metathesizing an unsaturated ester or cross-metathesizingtwo or more unsaturated esters. In such embodiments, the composition caninclude small quantities of the saturated (e.g., hydrogenated) variantsof the unsaturated esters used as reactants in the metathesis. Thecomposition can also include other saturated (e.g., hydrogenated)mono-ester byproducts of the metathesis reaction, e.g., from thenon-productive metathesis of the reactants with various alkenes andolefinic esters formed in the metathesis reactor.

In some embodiments, the dibasic ester is disposed in the reactor as acomponent of a composition. In some embodiments, the composition alsoincludes water or a substance that can release water. In someembodiments, the composition also includes an acid, such as a Bronsteador Lewis acid, which can serve to catalyze the reaction of the dibasicester with the water. Any suitable acid or combination of acids can beused. In some embodiments, for example, the acid is a water-solubleacid, such as a water-soluble Bronstead acid. In some embodiments, theacid is a water-soluble organic acid. In some other embodiments, theacid is a water-soluble inorganic acid. Suitable inorganic acidsinclude, but are not limited to: hydrohalic acids, such as hydrofluoricacid, hydrochloric acid, hydrobromic acid, and the like; otherhalogen-containing acids, such as perchloric acid, chloric acid,hypochlorous acid, hypofluorous acid, and the like; nitrogen-containingacids, such as nitric acid, nitrous acid, and the like;phosphorus-containing acids, such as phosphoric acid (as well asdihydrogen phosphates and hydrogen phosphates), phosphorous acid (aswell as hydrogen phosphites), hypophosphorous acid, and the like;boron-containing acids, such as boric acid and the like; andsulfur-containing acids, such as sulfuric acid (as well as hydrogensulfates), sulfurous acid (as well as hydrogen sulfites), and the like.Suitable organic acids include, but are not limited to, substituted andunsubstituted hydrocarbyl groups having a carboxylic acid group, aphenolic group, a sulfonic acid group, or other like groups. In someembodiments, no additional acid is added. In such embodiments, theformed dibasic acid can catalyze the reaction, although, in someembodiments, a small amount of the dibasic acid to be formed can be usedto seed the process. Further, in embodiments where the composition inthe reactor comprises one or more acids, one or more of those acids canbe homogeneous, meaning that they are at least partially solubilized bya liquid carrier (e.g., a solvent system). In some other embodiments,however, one or more of the acids are heterogeneous, meaning that theyare not solubilized by any liquid carrier. For example, in some suchembodiments, one or more of the acids can be disposed on a solidsupport, such as a polymeric support (e.g., polystyrene and the like) oran inorganic support (e.g., silica, alumina, and the like).

The method is not limited to any particular dibasic ester. In someembodiments, the dibasic ester is a compound having the formula:R—OOC—Y—COO—R′, wherein Y, R, and R′ denote any organic compound (suchas hydrocarbyl or silyl groups), including those bearing heteroatomcontaining substituent groups. In some such embodiments, R and R′ areindependently hydrocarbyl groups, which can be optionally substitutedwith various heteroatom-containing substituents, or whose carbon atomscan be replaced by one or more heteroatoms. Such hydrocarbyl groups caninclude substituted and unsubstituted alkyl, alkenyl, and oxyalkylgroups. In some such embodiments, Y is a divalent hydrocarbyl group,which can be optionally substituted with various heteroatom-containingsubstituents, or whose carbon atoms can be replaced by one or moreheteroatoms. Such divalent hydrocarbyl groups can include substitutedand unsubstituted alkylene, alkenylene, and oxyalkylene groups.

In some embodiments, the dibasic ester is a compound of formula (I):

wherein,

Y¹ is C₆₋₃₆ alkylene, C₆₋₃₆ alkenylene, C₆₋₃₆ heteroalkylene, or C₆₋₃₆heteroalkenylene, each of which is optionally substituted one or moretimes by substituents selected independently from R³;

R¹ and R² are independently C₁₋₁₂ alkyl, C₁₋₁₂ heteroalkyl, C₂₋₁₂alkenyl, or C₂₋₁₂ heteroalkenyl, each of which is optionally substitutedone or more times by substituents selected independently from R³; and

R³ is a halogen atom, —OH, —NH₂, C₁₋₆ alkyl, C₁₋₆ heteroalkyl, C₂₋₆alkenyl, C₂₋₆ heteroalkenyl, C₃₋₁₀ cyclokalkyl, or C₂₋₁₀heterocycloalkyl.

In some embodiments, Y¹ is C₆₋₃₆ alkylene, C₆₋₃₆ alkenylene, or C₄₋₃₆oxyalkylene, each of which is optionally substituted one or more timesby substituents selected from the group consisting of a halogen atom,—OH, —O(C₁₋₆ alkyl), —NH₂, —NH(C₁₋₆ alkyl), and N(C₁₋₆alkyl)₂. In somefurther such embodiments, Y¹ is C₆₋₃₆ alkylene, C₆₋₃₆ alkenylene, orC₄₋₃₆ oxyalkylene, each of which is optionally substituted one or moretimes by —OH. In some further such embodiments, Y¹ is —(CH₂)₈—,—(CH₂)₉—, —(CH₂)₁₀—, —(CH₂)₁₁—, —(CH₂)₁₂—, —(CH₂)₁₃—, —(CH₂)₁₄—,—(CH₂)₁₅—, —(CH₂)₁₆—, —(CH₂)₁₇—, —(CH₂)₁₈—, —(CH₂)₁₉—, —(CH₂)₂₀—,—(CH₂)₂₁—, or —(CH₂)₂₂—. In some embodiments, Y¹ is —(CH₂)₉—. In someembodiments, Y¹ is —(CH₂)₁₂—. In some embodiments, Y¹ is —(CH₂)₁₆—.

In some embodiments, R¹ and R² are independently C₁₋₈ alkyl, C₂₋₈alkenyl, or C₁₋₈ oxyalkenyl, each of which is optionally substituted oneor more times by —OH. In some further embodiments, R¹ and R² areindependently methyl, ethyl, propyl, isopropyl, butyl, isobutyl,sec-butyl, tert-butyl, pentyl, tert-pentyl, neopentyl, hexyl, or2-ethylhexyl. In some further embodiments, R¹ and R² are independentlymethyl, ethyl, or isopropyl. In some embodiments, R¹ and R² are bothmethyl.

In some embodiments, the dibasic ester is undecanedioic acid dimethylester. In some embodiments, the dibasic ester is tetradecanedioic aciddimethyl ester. In some embodiments, the dibasic ester isoctadecanedioic acid dimethyl ester.

Any suitable amount of the dibasic ester can be disposed in the reactor.In some embodiments, at least 50 grams, or at least 100 grams, or atleast 150 grams, or at least 200 grams, are introduced to the reactor.

Any suitable reactor can be used for introducing the dibasic ester. Insome embodiments, the reactor is a pressurizable reactor. In some suchembodiments, the reactor includes a sealable reaction vessel that canhold a pressure up to about 5 bar, or up to about 10 bar, or up to about20 bar, or up to about 30 bar, or up to about 40 bar, or up to about 50bar, or up to about 75 bar, or up to about 100 bar. In some embodiments,the reactor is equipped with a means of heating its contents. Thus, insome embodiments, the reactor can include one or more heating elementsdisposed proximate to the reaction vessel. Any suitable heating elementscan be used, including, but not limited to, electric wires (e.g.,electric heating coils), thermocouples, gas burners, heating blocks,pipes containing heated fluids (e.g., steam pipes, hot oil pipes, etc.),and the like. In some embodiments, one or more suitable heating elementscan be included on the inside of the reaction vessel. In someembodiments, such internal heating elements can be the sole means usedfor heating the reactor contents. In other embodiments, however, suchinternal heating elements can be used in addition to one or moreexternal heating elements. Because such internal heating elements may bein contact with the reactor contents, in some embodiments, the internalheating element is designed such that it can operate when in physicalcontact with one or more of the reactor contents. For example, in someembodiments, such internal heating elements include, but are not limitedto, electric wires (e.g., electric heating coils), thermocouples, pipescontaining heated fluids (e.g., steam pipes, hot oil pipes, etc.), andthe like.

The reaction vessel can have any suitable volume and/or shape, dependingon the certain factors, including, but not limited to, the nature of thereactants and products, the desired reaction temperature and pressure,the quantities of reactants. In some embodiments, the reaction vessel isa 600 mL Hastelloy C Parr reactor. In some other embodiments, thereaction vessel is a Hastelloy C pressure reactor, e.g., having a volumeof 500 L to 9000 L.

In some embodiments, the reaction vessel can include various devices orstructures to assist with fluid flow. Such devices or structures caninclude, but are not limited to, baffles, stirrers, stir bars,impellers, and the like. These elements can be disposed in the reactorin any suitable manner, depending on the desired reaction conditions,the nature of the reactor contents, and on other factors.

The reactor can also include various inlets and outlets for adding orremoving fluids (including gases and/or liquids) from the reactor. Insome embodiments, the reactor includes an inlet suitable for adding aliquid medium to the reactor. In some such embodiments, this liquidinlet is in fluid communication with a vessel containing said liquidmedium. In some such embodiments, one or more pumps can be disposedbetween the liquid-containing vessel and the inlet. Any pumps suitablefor pumping a liquid medium can be used. In some embodiments, the liquidmedium is an aqueous medium, such as water. In some embodiments, thereactor includes an outlet suitable for removing a gaseous medium fromthe reaction vessel. In some embodiments, said gas outlet is in fluidcommunication with a receiving vessel. In some embodiments, thereceiving vessel is a condenser, or is disposed proximate to one or morecooling elements, such that one or more of the substances contained inany gaseous stream can be condensed to a liquid. In some suchembodiments, one or more pressure regulators are disposed between thereceiving vessel and the gaseous outlet. Any suitable regulators can beused, so long as they can allow release of one or more gaseous speciesfrom the reactor without inducing a substantial reduction of reactorpressure. In some embodiments, the reactor may also include a gaseousinlet, such as a gaseous inlet that can be used for adding one or moregases (e.g., inert gases or non-reacting gases) to the reactor. Such aninlet can be used to sparge the reactor, e.g., during the course of thereaction. Or, in some other instances, it can be used to flush thereactor of undesired species, e.g., to flush the reactor of oxidants,such as oxygen. In some embodiments, the gas inlet is suitable fordelivery of certain inert gases to the reactor, either before, during,and/or after the reaction. Such inert gases include, but are not limitedto, nitrogen, helium, neon, argon, methane (flared), carbon dioxide, andthe like.

The methods include reacting the dibasic ester with water in the reactorto form a dibasic acid and an alcohol. The dibasic ester can be adibasic ester according to any of the above embodiments. Accordingly, insome embodiments, the resulting dibasic acid is a compound having theformula: H—OOC—Y—COO—H, wherein Y denotes any organic compound (such ashydrocarbyl or silyl groups), including those bearing heteroatomcontaining substituent groups. In some such embodiments, Y is a divalenthydrocarbyl group, which can be optionally substituted with variousheteroatom-containing substituents, or whose carbon atoms can bereplaced by one or more heteroatoms. Such divalent hydrocarbyl groupscan include substituted and unsubstituted alkylene, alkenylene, andoxyalkylene groups. In some such embodiments, the reaction also yieldsone or more alcohols. In some embodiments, the alcohols are compoundshaving the formulas: R—OH and R′—OH, where R and R′ denote any organiccompound (such as hydrocarbyl or silyl groups), including those bearingheteroatom containing substituent groups. In some such embodiments, Rand R′ are independently hydrocarbyl groups, which can be optionallysubstituted with various heteroatom-containing substituents, or whosecarbon atoms can be replaced by one or more heteroatoms. Suchhydrocarbyl groups can include substituted and unsubstituted alkyl,alkenyl, and oxyalkyl groups.

In some embodiments, the reaction forms a dibasic acid of formula (II)and alcohols of formula (IIIa) and formula (IIIb):

wherein,

Y¹ is C₆₋₃₆ alkylene, C₆₋₃₆ alkenylene, C₆₋₃₆ heteroalkylene, or C₆₋₃₆heteroalkenylene, each of which is optionally substituted one or moretimes by substituents selected independently from R³;

R¹ and R² are independently C₁₋₁₂ alkyl, C₁₋₁₂ heteroalkyl, C₂₋₁₂alkenyl, or C₂₋₁₂ heteroalkenyl, each of which is optionally substitutedone or more times by substituents selected independently from R³; and

R³ is a halogen atom, —OH, —NH₂, C₁₋₆ alkyl, C₁₋₆ heteroalkyl, C₂₋₆alkenyl, C₂₋₆ heteroalkenyl, C₃₋₁₀ cyclokalkyl, or C₂₋₁₀heterocycloalkyl.

In some embodiments, Y¹ is C₆₋₃₆ alkylene, C₆₋₃₆ alkenylene, or C₄₋₃₆oxyalkylene, each of which is optionally substituted one or more timesby substituents selected from the group consisting of a halogen atom,—OH, —O(C₁₋₆ alkyl), —NH₂, —NH(C₁₋₆ alkyl), and N(C₁₋₆alkyl)₂. In somefurther such embodiments, Y¹ is C₆₋₃₆ alkylene, C₆₋₃₆ alkenylene, orC₄₋₃₆ oxyalkylene, each of which is optionally substituted one or moretimes by —OH. In some further such embodiments, Y¹ is —(CH₂)₈—,—(CH₂)₈—, —(CH₂)₁₀—, —(CH₂)₁₁—, —(CH₂)₁₂—, —(CH₂)₁₃—, —(CH₂)₁₄—,—(CH₂)₁₅—, —(CH₂)₁₆—, —(CH₂)₁₇—, —(CH₂)₁₈—, —(CH₂)₁₉—, —(CH₂)₂₀—,—(CH₂)₂₁—, or —(CH₂)₂₂—. In some embodiments, Y¹ is —(CH₂)₉—. In someembodiments, Y¹ is —(CH₂)₁₂—. In some embodiments, Y¹ is —(CH₂)₁₆—.

In some embodiments, R¹ and R² are independently C₁₋₈ alkyl, C₂₋₈alkenyl, or C₁₋₈ oxyalkenyl, each of which is optionally substituted oneor more times by —OH. In some further embodiments, R¹ and R² areindependently methyl, ethyl, propyl, isopropyl, butyl, isobutyl,sec-butyl, tert-butyl, pentyl, tert-pentyl, neopentyl, hexyl, or2-ethylhexyl. In some further embodiments, R¹ and R² are independentlymethyl, ethyl, or isopropyl. In embodiments, R¹ and R² are both methyl.

In some embodiments, the dibasic acid is undecanedioic acid. In someembodiments, the dibasic ester is tetradecanedioic acid. In someembodiments, the dibasic ester is octadecanedioic acid. In someembodiments, the alcohols are selected from the group consisting of:methanol, ethanol, isopropanol, and mixtures thereof. In some suchembodiments, the alcohols are both methanol.

The water used in the reaction can be any suitable form of water,including but not limited to, distilled water, deionized water, and thelike. In some embodiments, deionized water is used. In some embodiments,an excess of water is used relative to the dibasic ester. In someembodiments, the initial mole-to-mole ratio of water to the dibasic acidin the reactor is from 1:1 to 25:1, or from 2:1 to 20:1, or from 3:1 to15:1.

The reaction can be carried out in any suitable reactor and under anysuitable conditions. In some embodiments, the reactor is a reactoraccording to any of the embodiments described above. In someembodiments, the reaction is carried out at an elevated temperature,e.g., at a temperature above 25° C. In some embodiments, the reaction iscarried out at a temperature (or at temperatures) from 50° C. to 500°C., or from 100° C. to 300° C., or from 150° C. to 300° C., or from 200°C. to 250° C. In some embodiments, the reaction is carried out at atemperature of about 225° C. In some embodiments, the reaction can becarried out at an elevated pressure, e.g., at a pressure above about 1bar. In some embodiments, the reaction is carried out at a pressure of 1barg to 50 barg, or from 10 barg to 40 barg. In some embodiments, thereaction is carried out at a pressure of about 25 barg. As used herein,the “barg” refers to the pressure in bar above atmospheric pressure.Thus, if atmospheric pressure is about 1 bar, then 25 barg roughlycorresponds to 26 bar pressure. Further, the reaction can be carried outfor any suitable duration, depending on a variety of factors, including,but not limited to, the reactor design, the quantity of material beingreacted, the temperature, pressure, and the like. In some embodiments,the reaction time is 2 to 12 hours, or 4 to 10 hours. In someembodiments, the reaction duration is about 5 hours, or about 6 hours,or about 7 hours, or about 8 hours, or about 9 hours, or about 10 hours,or about 11 hours, or about 12 hours.

In some embodiments, various species can be added and/or removed duringthe course of the reaction, e.g., to maintain the pressure, to increaseyield, etc. In some embodiments, an inert gas or non-reacting gas isadded during the course of the reaction. Suitable inert gases include,but are not limited to, gases that are non-condensing under typicalreaction conditions, such as nitrogen, helium, neon, argon, methane(flared), carbon dioxide, or mixtures thereof. The addition can becarried out in various ways. For example, in some embodiments, theaddition can be carried out in one or more discontinuous intervals. Or,in some other embodiments, the addition can be carried out continuously.Any suitable flow rate can be used. For example, in some embodiments,the inert gas can be continuously supplied to the reactor at a flow rateof 100 to 2000 sccm, or from 250 to 1500 sccm. Note, as used herein,“sccm” refers to standard cubic centimeters per minute, where thestandard is at 21° C. and 1 atm pressure). In some embodiments, the flowrate can be set to achieve a certain residence time under the givenreaction conditions (e.g., temperature, pressure, etc.). In some suchembodiments, the residence time of the added gas is from 10 minutes to24 hours, or 10 minutes to 12 hours, or 10 minutes to 4 hours, or 10 to60 minutes. In some embodiments, the added gas is permanently presentduring the reaction.

In some embodiments, additional water can be added during the course ofthe reaction. The addition can be carried out in various ways. Forexample, in some embodiments, the addition can be carried out in one ormore discontinuous intervals. Or, in some other embodiments, theaddition can be carried out continuously. Any suitable amount of watercan be added to the reactor during the course of the reaction. Asdiscussed in more detail below, in some embodiments, an amount of theformed alcohols is removed from the reactor during the course of thereaction. In some such embodiments, the amount of water added to thereactor during the course of the reaction is the amount of water (e.g.,mass of water) approximately equivalent to the total mass of thealcohols removed from the reactor during the course of the reaction. Forexample, in some embodiments, the mass-to-mass ratio of water added tothe reactor during the course of the reaction to alcohol removed fromthe reactor during the course of the reaction is from 0.7:1 to 1.3 to 1,or from 0.8:1 to 1.2:1, or from 0.9:1 to 1.1:1. In some embodiments, theratio is about 1:1. The water can be added in any suitable manner. Inembodiments where the reactor includes a liquid inlet (described above),the water is, in some such embodiments, introduced into the reactor viathe liquid inlet. As discussed above, any suitable form of water can beused, including, but not limited to, distilled water, deionized water,and the like. In some embodiments, the water is deionized water.

In some embodiments, at least a portion of the formed alcohols areremoved from the reactor during the course of the reaction. The removalcan be carried out in any suitable way. For example, in someembodiments, such as where an appreciable amount of the formed alcoholsare present in the reactor in the vapor phase, the removal can becarried out by venting the reactor, e.g., by venting the headspace. Insome embodiments, the removal occurs via a gas outlet in the reactor(described above). Further, in some embodiments, the removal can becarried out in one or more discontinuous intervals (e.g., every 15minutes, or every 30 minutes, or every 45 minutes, etc.). Or, in someother embodiments, the addition can be carried out continuously orsemi-continuously (e.g., where alcohols are being removed for at least50% of the time during when the reaction is occurring). Any suitableamount of alcohols can be removed from the reactor during the course ofthe reaction. In some embodiments, at least 30% by weight, or at least40% by weight, or at least 50% by weight, or at least 60% by weight, orat least 70% by weight, or at least 80% by weight, or at least 90% byweight, of the formed alcohols are removed from the reactor during thereaction. In some embodiments, the reaction can be run so as to achievea certain residence time for the reactants (i.e., the dibasic ester andthe water). In some embodiments, the residence time for the dibasicester is 1 to 12 hours, or 2 to 8 hours, or 3 to 6 hours. In someembodiments, the residence time for the dibasic ester is about 4 hours.In some embodiments, the residence time for the water is 10 minutes to12 hours, or 15 minutes to 6 hours, or 30 minutes to 3 hours. In someembodiments, the residence time for the water is about 1 hour.

In some embodiments, for example, to improve the yield, it may bedesirable to ensure that the amount of formed alcohols relative to waterin the reactor not rise above a certain ratio (e.g., by removal of theformed alcohols, described above). Thus, in some embodiments, thereaction is carried out such that the mole-to-mole ratio of water toformed alcohols is at least 1:1, or at least 2:1, or at least 3:1, or atleast 4:1, or at least 5:1.

It was discovered that the moving of the alcohols from the reactorduring the course of the reaction resulted in certain unexpectedimprovements over traditional hydrolysis methods. For example, theremoval of the alcohols caused a dramatic reduction in reaction time,which, in turn, resulted in a product that contained far fewerimpurities, such as colored impurities. There may also be fewermonobasic acid impurities in the resulting composition. In someinstances, the yield was improved as well. Due to these improvements, itmay be possible to reduce the amount of post-synthesis purification thatmust be carried out, thereby reducing the cost of making the product.

In some instances, it can be desirable to maintain a low amount ofoxygen in the reactor during the reaction. Oxygen can be removed by anysuitable means. For example, in some embodiments, the reactor can bepurged with an inert gas or non-reactive gas (e.g., nitrogen, helium,neon, argon, methane, carbon dioxide, and the like) near the start ofthe reaction or even before the reaction begins. In some embodiments,the concentration of oxygen in the reactor during the reaction is keptto a concentration of no more than 500 ppm, or no more than 250 ppm, orno more than 100 ppm, or no more than 50 ppm, or no more than 10 ppm. Insome embodiments, the purging gas is permanently present during thereaction.

Such reactions can often lead to the formation of colored impurities. Asused herein, the term “colored impurities” refers to compounds thatabsorb light having a wavelength of 440 nm or 550 nm. Thus, these arecompounds that absorb light in the blue-violet or the green portions ofthe visible electromagnetic spectrum. In some embodiments, themole-to-mole ratio of formed dibasic acid to colored impurities is atleast 250:1, or at least 350:1, or at least 500:1, or at least 1000:1,or at least 2000:1. In some embodiments, the hydrolyzed composition canbe treated to lower even further the concentration of colored impuritiesin the composition. For example, in some such embodiments, thehydrolyzed composition can be decolorized, for example, by contactingthe composition with a decolorizing agent. Suitable decolorizing agentsinclude, but are not limited to, activated carbon, silica, silicates(e.g., magnesium silicates), clay, diatomaceous earth, and alumina. Insome embodiments, for example, decolorizing agent is added to thecomposition, and the decolorizing agent is subsequently filtered out.Or, in some alternative embodiments, the composition can be passedthrough a bed containing the decolorizing agent. Additional treatmentscan also be carried out, either in addition to decolorization or insteadof decolorization. In some embodiments, the composition can be treatedwith a bleaching agent (e.g., an oxidizing agent), followed by anextraction to remove the bleaching agent from the composition.

In some embodiments, the dibasic acid may be subjected to additionalpurification, for example, using any of the embodiments of thepurification methods described below. In some other embodiments,however, such additional purification may be unnecessary.

In some embodiments, the methods described herein can lead to relativelyhigh conversion percentages, e.g., the percentage of dibasic esterconverted to dibasic acid. In some embodiments, at least 75%, or atleast 80%, or at least 90%, or at least 95%, or at least 97%, or atleast 99%, of the dibasic ester is converted to dibasic acid within theduration of the reaction. Further, in some embodiments, the amount ofdibasic ester converted to a dibasic monoacid/monoester (e.g., a dibasicester which reacts in such a way that, in the product, only one of thetwo ester groups has been converted to an acid). Thus, in someembodiments, the mole-to-mole ratio of dibasic acid to dibasicmonoacid/monoester in the product is at least 25:1, or at least 35:1, orat least 50:1, or at least 100:1, or at least 200:1, or at least 300:1.

Once the dibasic acid is obtained in the desired purity, the solid canbe dried. Any suitable drying technique can be used. For example, insome embodiments, the sample is dried in a drying unit, such as a rotarydryer. The dried material can be packaged in any suitable form,including, but not limited to, pellets, flakes, pastels, and the like.

FIG. 1 shows an illustrative embodiment of a method for hydrolyzing adibasic ester to a dibasic acid. The method 100 includes: introducing adibasic ester to a reactor 101; and reacting the dibasic ester withwater in the reactor 102 to form a dibasic acid and one or morealcohols. In some embodiments, at least a portion of the formed one ormore alcohols is removed from the reactor during the reacting. In someembodiments, the mole-to-mole ratio of formed dibasic acid to coloredimpurities is at least 250:1.

Hydrolysis Reactors

In certain aspects, the disclosure provides hydrolysis reactors,comprising: a pressurizable vessel, wherein the pressurizable vesselcomprises an inlet and an outlet; a water source, wherein the watersource is in fluid communication with the inlet of the pressurizablevessel; and a receiving unit, wherein the receiving unit is in fluidcommunication with the gas outlet of the pressurizable vessel.

The reactors include a pressurizable vessel. In some embodiments, thepressurizable reactor is a sealable vessel that can hold a pressure upto about 5 bar, or up to about 10 bar, or up to about 20 bar, or up toabout 30 bar, or up to about 40 bar, or up to about 50 bar, or up toabout 75 bar, or up to about 100 bar. In some embodiments, the reactoris equipped with a means of heating its contents. Thus, in someembodiments, the reactor can include one or more heating elementsdisposed proximate to the reaction vessel. Such heating elements can bedisposed on the interior or the exterior of the reactor. Any suitableheating elements can be used, including, but not limited to, electricwires (e.g., electric heating coils), thermocouples, gas burners,heating blocks, pipes containing heated fluids (e.g., steam pipes, hotoil pipes, etc.), and the like. In some embodiments, one or moresuitable heating elements can be included on the inside of the reactionvessel. In some embodiments, such internal heating elements can be thesole means used for heating the reactor contents. In other embodiments,however, such internal heating elements can be used in addition to oneor more external heating elements. Because such internal heatingelements may be in contact with the reactor contents, in someembodiments, the internal heating element is designed such that it canoperate when in physical contact with one or more of the reactorcontents. For example, in some embodiments, such internal heatingelements include, but are not limited to, electric wires (e.g., electricheating coils), thermocouples, pipes containing heated fluids (e.g.,steam pipes, hot oil pipes, etc.), and the like. In some otherembodiments, the reactor can include a steam injection port to allow forheating by direct steam injection.

The reaction vessel can have any suitable volume and/or shape, dependingon the certain factors, including, but not limited to, the nature of thereactants and products, the desired reaction temperature and pressure,the quantities of reactants. In some embodiments, the reaction vessel isa 600 mL Hastelloy C Parr reactor. In some other embodiments, thereaction vessel is a Hastelloy C pressure reactor, e.g., having a volumeof 500 L to 9000 L.

In some embodiments, the reaction vessel can include various devices orstructures to assist with fluid flow. Such devices or structures caninclude, but are not limited to, baffles, stirrers, stir bars,impellers, and the like. These elements can be disposed in the reactorin any suitable manner, depending on the desired reaction conditions,the nature of the reactor contents, and on other factors.

The reactors include an inlet and a water source, wherein the watersource is in fluid communication with the inlet of the pressurizablevessel. The water source can be any suitable means for delivering water.In some embodiments, the water source is a tank. In some embodiments,the water source is a vessel suitable for holding liquid media. In someother embodiments, the water source is a tap. In some embodiments, oneor more pumps can be disposed between the water source and the inlet.Any pumps suitable for pumping water can be used. The water in the watersource can be any suitable form of water, including but not limited to,distilled water, deionized water, and the like. In some embodiments, thewater is deionized water. In some other embodiments, the water inlet canbe a steam injection port, where, for example, steam can be used toprovide the reactant and to provide a hear source or a partial heatsource for the reaction. In such embodiments, the port should be capableof injecting steam at a pressure of 500 to 1000 prig.

The reactors include an outlet, which is in fluid communication with areceiving unit. In some embodiments, the outlet is an outlet suitablefor releasing or removing gaseous species from the reactor, e.g., duringthe course of a reaction. In some such embodiments, the receiving unitor vessel is a condenser, or is disposed proximate to one or morecooling elements, such that one or more of the substances contained inany gaseous stream removed from the reactor can be condensed to aliquid. In some such embodiments, one or more pressure regulators aredisposed between the receiving unit and the gaseous outlet. Any suitableregulators can be used, so long as they can allow release of one or moregaseous species from the reactor without inducing a substantialreduction of reactor pressure. In some embodiments, such regulatorsshould be capable of maintaining a pressure up to about 5 bar, or up toabout 10 bar, or up to about 20 bar, or up to about 30 bar, or up toabout 40 bar, or up to about 50 bar, or up to about 75 bar, or up toabout 100 bar. In some embodiments, the pressure regulator isadjustable.

In some embodiments, the system could include a separator (e.g., a flashpan), which can be used, for example, to separate water in the condensedfluid from other materials in the condensed fluid (e.g., ester).

In some embodiments, the reactor may also include a gaseous inlet, suchas a gaseous inlet that can be used for adding one or more gases (e.g.,inert gases or non-reactive gases) to the reactor. Such an inlet can beused to sparge the reactor, e.g., during the course of the reaction. Or,in some other instances, it can be used to flush the reactor ofundesired species, e.g., to flush the reactor of oxidants, such asoxygen. In some embodiments, the gas inlet is suitable for delivery ofcertain inert gases to the reactor, either before, during, and/or afterthe reaction. Such inert gases or non-reactive gases include, but arenot limited to, nitrogen, helium, neon, argon, methane, carbon dioxide,and the like.

The reactor can also include various temperature and pressure detectors.Any suitable detectors can be used, depending on the environment inwhich it is placed and the temperature or pressure values it is intendedto measure. For example, in some embodiments, the reaction vesselincludes an internal temperature detector that measures the temperaturein at least one location within the reactor. In some embodiments, thereaction vessel includes a pressure detector, for example, disposed inthe headspace of the reactor. In some such embodiments, the pressuredetector can be disposed adjacent to the gas outlet. In someembodiments, the receiving unit (e.g., condenser) can also include atemperature detector, either internal to the unit or external. In someembodiments, where a fluid line connects the gas outlet to the receivingunit, one or more temperature detectors can be disposed adjacent to saidfluid line. Other temperature or pressure detectors can be disposed atvarious other locations in the reactor. For example, it may be desirableto include multiple temperature detectors in the reactor.

FIG. 2 shows an illustrative embodiment of a reactor disclosed herein.The reactor 200 includes a reaction vessel 201, a heating block 202,baffles 203, a stirrer 204, a liquid inlet 205 in fluid communication toa water source 206 via a pump 207, an adjustable gas inlet 208 equippedwith a flow meter 209, a gas outlet 210 in fluid communication with acondenser 211 having a cooling jacket 212 via an adjustable pressureregulator 213.

A reactor according to any of the aforementioned embodiments can be usedto carry out the previously described methods of hydrolyzing a dibasicester.

In some embodiments, the reaction can be run as an autocatalyticreaction wherein a portion of the dibasic acid product is seeded in thereactor (or recycled from a previous batch) to increase the reactionrate in the beginning of the reactor train. For example, in embodimentswhere batch reactions are carried out, the residence time may be reducedby leaving a portion of dibasic acid product in the reactor from onebatch for use in the next batch. In some embodiments, multiplecontinuous reactors in series could be used. For example, two continuousstirred tank reactors (CSTRs) in series could be applied, where aportion of the product from the second reactor is recycled to the firstreactor to maintain a high acid concentration in the first reactor. Insome such embodiments, the high acid concentration would reduce thereaction time, potentially resulting in a smaller reactor size for thefirst reactor.

Methods of Purifying a Dibasic Acid Composition

In certain aspects, the disclosure provides methods of forming apurified solid-state dibasic acid composition, comprising: providing afirst composition, which comprises a first amount of dibasic acid and afirst amount of one or more monobasic acids, each dissolved in a solventsystem; and cooling the first composition to form a second composition,which comprises a second amount the dibasic acid in solid-state formsuspended in the solvent system, and a second amount of the one or moremonobasic acids dissolved in the solvent system.

In certain embodiments, the methods include providing a firstcomposition that includes a first amount of a dibasic acid and a firstamount of one or more monobasic acids dissolved in a solvent system. Asused herein, “providing” is to be given its broadest reasonableinterpretation. For example, as used herein, providing can includegenerating a composition, but can also include receiving such acomposition after it has already been generated.

Any suitable solvent system can be used, so long as at least a portionof the dibasic acid and the one or more monobasic acids are solubilizedby the solvent system.

Suitable solvent systems include, but are not limited to, solventsystems comprising toluene, ortho-xylene, meta-xylene, para-xylene,acetone, dimethylformamide, tetrahydrofuran, methylene dichloride,dimethyl sulfoxide, or any mixture thereof. In some embodiments, thesolvent system comprises toluene, ortho-xylene, meta-xylene,para-xylene, or any mixtures thereof. In some further embodiments, thesolvent system comprises toluene. In some such embodiments, the solventsystem is predominantly toluene, e.g., at least 50% by volume, or atleast 70% by volume, or at least 80% by volume, or at least 90% byvolume toluene.

The dibasic acid need not be entirely solubilized by the solvent system,as long as at least a portion is solubilized by the solvent system. Forexample, in some embodiments, at least 70%, or at least 80%, or at least90%, or at least 95%, or at least 98% of the dibasic acid is solubilizedby the solvent system.

Further, the composition can also include some amount of monobasic acidthat is not solubilized by the solvent system. In such instances, thenon-solubilized monobasic acid may be suitable separated from thecomposition by any suitable means.

In some embodiments, the initial composition is at a temperature aboveroom temperature (e.g., above 25° C.). In some embodiments, the initialcomposition is at a temperature of 40° C. to 120° C., or of 50° C. to100° C. In some embodiments, the initial composition is at a temperaturenot more than 20° C., or not more than 10° C., or not more than 5° C.higher than the temperature at which at least 95% of the dibasic acid issolubilized by the solvent system.

The initial composition can be disposed in any suitable vessel. Incertain embodiments, the vessel is a vessel suitable for carrying outthe recrystallization of organic compounds. In some embodiments, thevessel is a glass vessel, such as a glass filter reactor. In someembodiments, the vessel is also equipped with a reflux apparatus, suchas a reflux condenser. In some other embodiments, the vessel can bedisposed proximate to a heat source, such as a gas burner, heatingblock, electric wire (e.g., coil), pipes containing heated fluids, andthe like. In some further embodiments, the vessel can also be equippedwith an apparatus for carrying out nitrogen blanketing. In someembodiments, the vessel is equipped with a heat exchange medium that iscapable of both heating and/or cooling. For example, in someembodiments, a jacketed vessel with a heat transfer fluid that iscirculated and capable of being cooled by a refrigeration system andheated by electric, resistive heating.

The dibasic acid can be a dibasic acid according to any of the aboveembodiments. In some embodiments, the dibasic acid is a compound havingthe formula: H—OOC—Y—COO—H, wherein Y denotes any organic compound (suchas hydrocarbyl or silyl groups), including those bearing heteroatomcontaining substituent groups. In some such embodiments, Y is a divalenthydrocarbyl group, which can be optionally substituted with variousheteroatom-containing substituents, or whose carbon atoms can bereplaced by one or more heteroatoms. Such divalent hydrocarbyl groupscan include substituted and unsubstituted alkylene, alkenylene, andoxyalkylene groups.

In some embodiments, the dibasic acid is a compound of formula (II):

wherein,

Y¹ is C₆₋₃₆ alkylene, C₆₋₃₆alkenylene, C₆₋₃₆ heteroalkylene, or C₆₋₃₆heteroalkenylene, each of which is optionally substituted one or moretimes by substituents selected independently from R³;

R³ is a halogen atom, —OH, —NH₂, C₁₋₆alkyl, C₁₋₆ heteroalkyl, C₂₋₆alkenyl, C₂₋₆ heteroalkenyl, C₃₋₁₀ cyclokalkyl, or C₂₋₁₀heterocycloalkyl.

In some embodiments, Y¹ is C₆₋₃₆ alkylene, C₆₋₃₆alkenylene, or C₄₋₃₆oxyalkylene, each of which is optionally substituted one or more timesby substituents selected from the group consisting of a halogen atom,—OH, —O(C₁₋₆alkyl), —NH₂, —NH(C₁₋₆alkyl), and N(C₁₋₆alkyl)₂. In somefurther such embodiments, Y¹ is C₆₋₃₆ alkylene, C₆₋₃₆alkenylene, orC₄₋₃₆ oxyalkylene, each of which is optionally substituted one or moretimes by —OH. In some further such embodiments, Y¹ is —(CH₂)₈—,—(CH₂)₈—, —(CH₂)₁₉—, —(CH₂)₁₁—, —(CH₂)₁₂—, —(CH₂)₁₃—, —(CH₂)₁₄—,—(CH₂)₁₅ ^(˜), —(CH₂)₁₆—, —(CH₂)₁₂—, —(CH₂)₁₈—, —(CH₂)₁₉—, —(CH₂)₂₀—,—(CH₂)₂₁—, or —(CH₂)₂₂—. In some embodiments, Y¹ is —(CH₂)₉—. In someembodiments, Y¹ is —(CH₂)₁₂—. In some embodiments, Y¹ is —(CH₂)₁₆—.

In some embodiments, the dibasic acid is undecanedioic acid. In someembodiments, the dibasic ester is tetradecanedioic acid. In someembodiments, the dibasic ester is octadecanedioic acid.

The methods include cooling the initial composition to form a secondcomposition, which comprises a second amount the dibasic acid insolid-state form suspended in the solvent system, and a second amount ofthe one or more monobasic acids dissolved in the solvent system. Thecooling can be carried out by any suitable means and at any suitablerate. In some embodiments, for example, the cooling is effected byremoving the vessel from the heat source (or turning the heat sourceoff), and allowing the composition to cool from an elevated temperatureto room temperature. In some other embodiments, the composition can becooled from a first (higher) elevated temperature and cooled to a second(lower) elevated temperature. In some such embodiments, the compositioncan be held at the second elevated temperature for a certain period oftime, such as 5-30 minutes, or 10-20 minutes, or about 15 minutes. Insome such embodiments, the first (higher) elevated temperature is 80° C.to 120° C., or 90° C. to 110° C., and the second (lower) temperature is30° C. to 70° C., or 40° C. to 60° C. The cooling of the composition canbe carried out at a rate of 0.5° C./minute to 2.0° C./minute, based onthe temperature of the composition. In some embodiments, the cooling ofthe composition is carried out at a rate of about 1° C./minute, based onthe temperature of the composition. In some other embodiments, thepurification can be carried out in multiple (e.g., two) vesselsspecialized for recrystallization, instead of using a single vessel.

The second composition comprises an amount (i.e., a second amount) ofdibasic acid in solid-state form suspended in the solvent system. Asused herein, “suspended” or “suspend” or “suspension” are intended torefer broadly to any composition that includes a solid material (e.g.,crystals, particles, and the like) disposed in a liquid medium. The term“suspended” does not imply that the solid material be distributedhomogeneously within the liquid medium. For example, in someembodiments, the solid material may be disposed in the bottom portion ofthe vessel due to the force of gravity on the solid material. Thesuspension can be formed by any suitable means. In some embodiments, thesuspension is formed by precipitating the solid material out ofsolution, for example, by cooling the composition, or by employing othermeans of inducing precipitation (e.g., altering the polarity of thesolvent, and the like). In certain embodiments, at least 50%, or atleast 60%, or at least 70%, or at least 80%, or at least 90%, or atleast 95%, or at least 97% of the dibasic acid in the second compositionis in solid-state form suspended in the solvent system (as opposed tobeing solubilized by the solvent system).

The second composition also includes an amount (i.e., a second amount)of the one or more monobasic acids dissolved in the solvent system. Insome embodiments, at least 50%, or at least 60%, or at least 70%, or atleast 80% of the monobasic acids remain dissolved in the solvent system(as opposed to precipitating out as a solid with the dibasic acid).Thus, in such embodiments, the solid material (e.g., the solidprecipitate) in the second composition contains a highly pure form ofthe dibasic acid with a very small amount of monobasic acids. In someembodiments, monobasic acids make up less than 2 percent by weight, orless than 1.5 percent by weight, or less than 1 percent by weight, orless than 0.5 percent by weight of the solid-state material in thesecond composition, based on the total weight if solid-state materialsuspended in the solvent system in the second composition.

In some embodiments, the precipitated solid material in the secondcomposition can be separated from the solvent system of the secondcomposition, and washed with clean solvent. In such embodiments, thesolid-state material can be further dried to yield a highly puresolid-state form of the dibasic acid.

The monobasic acids described above can include organic acids, but canalso include dibasic monoesters/monoacids (e.g., that were formed due toincomplete hydrolysis of the dibasic ester to a dibasic alcohol). Insome embodiments, the one or more monobasic acids are compounds offormula (IVa), compounds of formula (IVb), or any mixture thereof:

wherein:

Y² is C₆₋₃₆ alkylene, C₆₋₃₆ alkenylene, C₆₋₃₆ heteroalkylene, or C₆₋₃₆heteroalkenylene, each of which is optionally substituted one or moretimes by substituents selected independently from R⁶;

R⁵ is C₁₋₁₂ alkyl, C₁₋₁₂ heteroalkyl, C₂₋₁₂ alkenyl, or C₂₋₁₂heteroalkenyl, each of which is optionally substituted one or more timesby substituents selected independently from R⁶;

R⁶ is a halogen atom, —OH, —NH₂, C₁₋₆ alkyl, C₁₋₆ heteroalkyl, C₂₋₆alkenyl, C₂₋₆ heteroalkenyl, C₃₋₁₀ cyclokalkyl, or C₂₋₁₀heterocycloalkyl;

R⁸ is C₁₋₁₂ alkyl, C₁₋₁₂ heteroalkyl, C₂₋₁₂ alkenyl, or C₂₋₁₂heteroalkenyl, each of which is optionally substituted one or more timesby substituents selected independently from R⁹; and

R⁹ is a halogen atom, C₁₋₆ alkyl, C₁₋₆ heteroalkyl, C₂₋₆ alkenyl, C₂₋₆heteroalkenyl, C₆₋₁₄ aryl, C₂₋₁₄ heteroaryl, C₃₋₁₀ cyclokalkyl, or C₂₋₁₀heterocycloalkyl.

In some embodiments, Y² is C₆₋₃₆ alkylene, C₆₋₃₆ alkenylene, C₄₋₃₆oxyalkylene, each of which is optionally substituted one or more timesby substituents selected from the group consisting of a halogen atom,—OH, —O(C₁₋₆ alkyl), —NH₂, —NH(C₁₋₆ alkyl), and N(C₁₋₆alkyl)₂. In somefurther embodiments, Y² is C₆₋₃₆ alkylene C₆₋₃₆ alkenylene, or C₄₋₃₆oxyalkylene, each of which is optionally substituted one or more timesby —OH. In some even further embodiments, Y² is —(CH₂)₈—, —(CH₂)₉—,—(CH₂)₁₀—, —(CH₂)₁₁—, —(CH₂)₁₂—, —(CH₂)₁₃—, —(CH₂)₁₄—, —(CH₂)₁₅—,—(CH₂)₁₆ ^(˜), —(CH₂)₁₂—, —(CH₂)₁₈—, —(CH₂)₁₉—, —(CH₂)₂₀—, —(CH₂)₂₁—, or—(CH₂)₂₂—. In some embodiments, Y² is —(CH₂)₉—. In some embodiments, Y²is —(CH₂)₁₂—. In some embodiments, Y² is —(CH₂)₁₆—.

In some embodiments, R⁵ is C₁₋₁₄ alkyl, C₂₋₁₄ alkenyl, or C₂₋₁₄oxyalkyl, each of which is optionally substituted one or more times by—OH. In some further embodiments, R⁵ is methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, tert-pentyl,neopentyl, hexyl, or 2-ethylhexyl. In some even further embodiments, R⁵is methyl.

In some embodiments, R⁸ is C₁₋₁₄ alkyl, C₂₋₁₄ alkenyl, or C₂₋₁₄oxyalkyl, each of which is optionally substituted one or more times by—OH. In some further embodiments, R⁸ is heptyl, octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, orheptadecyl. In some even further embodiments, R⁸ is nonyl or undecyl.

FIG. 3 shows an illustrative embodiments for forming a purifiedsolid-state dibasic acid composition. The method 300 includes: providinga first composition 301, which comprises a first amount of dibasic acidand a first amount of monobasic acid, each dissolved in the solventsystem; and cooling the first composition 302 to form a secondcomposition, which comprises a second amount of the dibasic acid insolid-state form suspended in the composition, and a second amount ofthe one or more monobasic acids dissolved in solution.

Method of Forming a Dibasic Acid by Metathesis

In certain aspects, the disclosure provides methods of forming a dibasicacid, including: reacting a first olefin ester and an second olefinester in the presence of a metathesis catalyst to form a first alkeneand an unsaturated dibasic ester; hydrogenating the unsaturated dibasicester to form a saturated dibasic ester; and converting the saturateddibasic ester to a saturated dibasic acid.

The methods include reacting the first olefin ester with the secondolefin ester to form an unsaturated dibasic ester. Reactions of olefinicesters to make unsaturated dibasic esters are generally described in PCTPublication WO 2008/140468, and United States Patent ApplicationPublication Nos. 2009/0264672 and 2013/0085288, all three of which arehereby incorporated by reference as though fully set forth herein intheir entireties. If there is a direct or indirect contradiction betweensubject matter disclosed in the incorporated references and the presentdisclosure (e.g., definitions of the same term that differ in theirscope), the description in the present disclosure controls.

As noted below, in some embodiments, one or more of the reactants forthe metathesis reaction can be generated from a renewable source, e.g.,by refining a natural oil or a derivative thereof. In some embodiments,the refining process includes cross-metathesizing the natural oil or aderivative thereof with an alkene. In such instances, the reactants maynot be entirely pure, as certain other alkene and ester byproducts ofthe natural oil refining may be present in the input stream. Therefore,in some embodiments, the reactants can be subjected to a pre-treatment,such as a thermal pre-treatment, to remove certain impurities,including, but not limited to, water, volatile organics (esters andalkenes), and certain aldehydes.

Metathesis reactions can provide a useful synthetic tool for making newolefinic compounds from olefinic reactants. In general, metathesisinvolves an exchange of allylidene groups between two reacting olefincompounds. In some instances, the reacting compounds are the same, whichcan be referred to as a “self-metathesis” reaction. In other instances,however, the reacting compounds are different, which can be referred toas a “cross-metathesis reaction” reaction. Other types of metathesisreactions are also known.

Metathesis reactions can be carried out under any conditions adequate toproduce the desired metathesis products. For example, stoichiometry,atmosphere, solvent, temperature, and pressure can be selected by oneskilled in the art to produce a desired product and to minimizeundesirable byproducts. In some embodiments, the metathesis process maybe conducted under an inert atmosphere. Similarly, in embodiments were areagent is supplied as a gas, an inert gaseous diluent can be used inthe gas stream. In such embodiments, the inert atmosphere or inertgaseous diluent typically is an inert gas, meaning that the gas does notinteract with the metathesis catalyst to impede catalysis to asubstantial degree. For example, non-limiting examples of inert gases ornon-reactive gases include helium, neon, argon, nitrogen, methane(flared), and carbon dioxide, used individually or in with each otherand other inert gases or non-reacting gases.

Metathesis reactions, including those disclosed herein, can be carriedout in any suitable reactor, depending on a variety of factors. Relevantfactors include, but are not limited to, the scale of the reaction, theselection of conditions (e.g., temperature, pressure, etc.) the identityof the reacting species, the identity of the resulting products and thedesired product(s), and the identity of the catalyst. Suitable reactorscan be designed by those of skill in the art, depending on the relevantfactors, and incorporated into a reaction process such, such as thosedisclosed herein.

The metathesis reactions disclosed herein generally occur in thepresence of one or more metathesis catalysts. Such methods can employany suitable metathesis catalyst. The metathesis catalyst in thisreaction may include any catalyst or catalyst system that catalyzes ametathesis reaction. Any known metathesis catalyst may be used, alone orin combination with one or more additional catalysts. Examples ofmetathesis catalysts and process conditions are described in UnitedStates Patent Application Publication No. 2011/0160472, incorporated byreference herein in its entirety, except that in the event of anyinconsistent disclosure or definition from the present specification,the disclosure or definition herein shall be deemed to prevail. A numberof the metathesis catalysts described in United States PatentApplication Publication No. 2011/0160472 are presently available fromMateria, Inc. (Pasadena, Calif.).

In some embodiments, the metathesis catalyst includes a Grubbs-typeolefin metathesis catalyst and/or an entity derived therefrom. In someembodiments, the metathesis catalyst includes a first-generationGrubbs-type olefin metathesis catalyst and/or an entity derivedtherefrom. In some embodiments, the metathesis catalyst includes asecond-generation Grubbs-type olefin metathesis catalyst and/or anentity derived therefrom. In some embodiments, the metathesis catalystincludes a first-generation Hoveyda-Grubbs-type olefin metathesiscatalyst and/or an entity derived therefrom. In some embodiments, themetathesis catalyst includes a second-generation Hoveyda-Grubbs-typeolefin metathesis catalyst and/or an entity derived therefrom. In someembodiments, the metathesis catalyst includes one or a plurality of theruthenium carbene metathesis catalysts sold by Materia, Inc. ofPasadena, Calif. and/or one or more entities derived from suchcatalysts. Representative metathesis catalysts from Materia, Inc. foruse in accordance with the present teachings include but are not limitedto those sold under the following product numbers as well ascombinations thereof: product no. C823 (CAS no. 172222-30-9), productno. C848 (CAS no. 246047-72-3), product no. C601 (CAS no. 203714-71-0),product no. C627 (CAS no. 301224-40-8), product no. C571 (CAS no.927429-61-6), product no. C598 (CAS no. 802912-44-3), product no. C793(CAS no. 927429-60-5), product no. C801 (CAS no. 194659-03-9), productno. C827 (CAS no. 253688-91-4), product no. C884 (CAS no. 900169-53-1),product no. C833 (CAS no. 1020085-61-3), product no. C859 (CAS no.832146-68-6), product no. C711 (CAS no. 635679-24-2), product no. C933(CAS no. 373640-75-6).

In some embodiments, the metathesis catalyst includes a molybdenumand/or tungsten carbene complex and/or an entity derived from such acomplex. In some embodiments, the metathesis catalyst includes aSchrock-type olefin metathesis catalyst and/or an entity derivedtherefrom. In some embodiments, the metathesis catalyst includes ahigh-oxidation-state alkylidene complex of molybdenum and/or an entityderived therefrom. In some embodiments, the metathesis catalyst includesa high-oxidation-state alkylidene complex of tungsten and/or an entityderived therefrom. In some embodiments, the metathesis catalyst includesmolybdenum (VI). In some embodiments, the metathesis catalyst includestungsten (VI). In some embodiments, the metathesis catalyst includes amolybdenum- and/or a tungsten-containing alkylidene complex of a typedescribed in one or more of (a) Angew. Chem. Int. Ed. Engl., 2003, 42,4592-4633; (b) Chem. Rev., 2002, 102, 145-179; and/or (c) Chem. Rev.,2009, 109, 3211-3226, each of which is incorporated by reference hereinin its entirety, except that in the event of any inconsistent disclosureor definition from the present specification, the disclosure ordefinition herein shall be deemed to prevail.

In certain embodiments, the metathesis catalyst is dissolved in asolvent prior to conducting the metathesis reaction. In certain suchembodiments, the solvent chosen may be selected to be substantiallyinert with respect to the metathesis catalyst. For example,substantially inert solvents include, without limitation: aromatichydrocarbons, such as benzene, toluene, xylenes, etc.; halogenatedaromatic hydrocarbons, such as chlorobenzene and dichlorobenzene;aliphatic solvents, including pentane, hexane, heptane, cyclohexane,etc.; and chlorinated alkanes, such as dichloromethane, chloroform,dichloroethane, etc. In some embodiments, the solvent comprises toluene.

In other embodiments, the metathesis catalyst is not dissolved in asolvent prior to conducting the metathesis reaction. The catalyst,instead, for example, can be slurried with the natural oil orunsaturated ester, where the natural oil or unsaturated ester is in aliquid state. Under these conditions, it is possible to eliminate thesolvent (e.g., toluene) from the process and eliminate downstream olefinlosses when separating the solvent. In other embodiments, the metathesiscatalyst may be added in solid state form (and not slurried) to thenatural oil or unsaturated ester (e.g., as an auger feed).

The metathesis reaction temperature may, in some instances, be arate-controlling variable where the temperature is selected to provide adesired product at an acceptable rate. In certain embodiments, themetathesis reaction temperature is greater than −40° C., or greater than−20° C., or greater than 0° C., or greater than 10° C. In certainembodiments, the metathesis reaction temperature is less than 200° C.,or less than 150° C., or less than 120° C. In some embodiments, themetathesis reaction temperature is between 0° C. and 150° C., or isbetween 10° C. and 120° C.

The metathesis reaction can be run under any desired pressure. In someinstances, it may be desirable to maintain a total pressure that is highenough to keep the cross-metathesis reagent in solution. Therefore, asthe molecular weight of the cross-metathesis reagent increases, thelower pressure range typically decreases since the boiling point of thecross-metathesis reagent increases. The total pressure may be selectedto be greater than 0.1 atm (10 kPa), or greater than 0.3 atm (30 kPa),or greater than 1 atm (100 kPa). In some embodiments, the reactionpressure is no more than about 70 atm (7000 kPa), or no more than about30 atm (3000 kPa). In some embodiments, the pressure for the metathesisreaction ranges from about 1 atm (100 kPa) to about 30 atm (3000 kPa).

In some embodiments, the first olefin ester and the second olefin esterare both terminal olefin esters, meaning that they have a terminalcarbon-carbon double bond. In some such embodiments, the terminal olefinesters are independently compounds of formula (V):

wherein:

X¹ is C₃₋₁₈ alkylene, C₃₋₁₈ alkenylene, C₂₋₁₈ heteroalkylene, or C₂₋₁₈heteroalkenylene, each of which is optionally substituted one or moretimes by substituents selected independently from R¹²;

R¹¹ is C₁₋₁₂ alkyl, C₁₋₁₂ heteroalkyl, C₂₋₁₂ alkenyl, or C₂₋₁₂heteroalkenyl, each of which is optionally substituted one or more timesby substituents selected independently from R¹²; and

R¹² is a halogen atom, —OH, —NH₂, C₁₋₆ alkyl, C₁₋₆ heteroalkyl, C₂₋₆alkenyl, C₂₋₆ heteroalkenyl, C₃₋₁₀ cyclokalkyl, or C₂₋₁₀heterocycloalkyl.

In some such embodiments, X¹ is C₃₋₁₈alkylene, C₃₋₁₈alkenylene, or C₂₋₁₈oxyalkylene, each of which is optionally substituted one or more timesby substituents selected from the group consisting of a halogen atom,—OH, —O(C₁₋₆ alkyl), —NH₂, —NH(C₁₋₆ alkyl), and N(C₁₋₆ alkyl)₂. In somefurther embodiments, X¹ is C₃₋₁₈ alkylene, C₃₋₁₈ alkenylene, or C₂₋₁₈oxyalkylene, each of which is optionally substituted one or more timesby —OH. In some even further embodiments, X¹ is —(CH₂)₂—CH═,—(CH₂)₃—CH═, —(CH₂)₄—CH═, —(CH₂)₅—CH═, —(CH₂)₆—CH═, —(CH₂)₇—CH═,—(CH₂)₈—CH═, —(CH₂)₉—CH═, —(CH₂)₁₀—CH═, —(CH₂)₁₁—CH═, —(CH₂)₁₂—CH═,—(CH₂)₁₃—CH═, —(CH₂)₁₄—CH═, or —(CH₂)₁₅—CH═. In some even furtherembodiments, X¹ is —(CH₂)₇—CH═.

In some such embodiments, R¹¹ is C₁₋₈ alkyl, C₂₋₈ alkenyl, or C₁₋₈oxyalkyl, each of which is optionally substituted one or more times by—OH. In some further embodiments, R¹¹ is methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, tert-pentyl,neopentyl, hexyl, or 2-ethylhexyl. In some even further embodiments, R¹¹is methyl.

In some embodiments, the terminal olefin esters are different compounds.In some other embodiments, however, the terminal olefin esters are thesame compound. In some embodiments, the terminal olefins esters are bothesters of 9-decenoic acid, for example, in some further embodiments,both terminal olefin esters are 9-decenoic acid methyl ester.

When the terminal olefins esters react, an olefinic byproduct (e.g., analkene) is also produced. In some embodiments, where the terminal olefinesters react to form an unsaturated dibasic ester, the resulting alkeneis ethylene. The formed ethylene can be vented from the reactor duringthe course of the reaction, or can be allowed to stay in the reactor.Metathesis reactions that generate the desired unsaturated dibasicesters can be referred to as “productive metathesis,” as the catalyst isused to make the desired product. In some instances, however, twoterminal olefin esters can react in a way that simply regenerates twonew molecules of the same terminal olefin esters that served asreactants. Such metathesis reactions can be referred to as “unproductivemetathesis,” as the catalyst is used to make products besides thedesired unsaturated dibasic esters.

In some other embodiments, the first olefin ester and the second olefinester are both internal olefin esters. In some such embodiments, thefirst olefin ester and the second olefin ester are independentlycompounds of formula (VI):

wherein:

X² is C₃₋₁₈ alkylene, C₃₋₁₈ alkenylene, C₂₄₈ heteroalkylene, or C₂₄₈heteroalkenylene, each of which is optionally substituted one or moretimes by substituents selected independently from R¹⁵;

R¹³ is C₁₋₁₂ alkyl, C₁₋₁₂ heteroalkyl, C₂₋₁₂ alkenyl, or C₂₋₁₂heteroalkenyl, each of which is optionally substituted one or more timesby substituents selected independently from R¹⁵;

R¹⁴ is C₁₋₁₂ alkyl, C₁₋₁₂ heteroalkyl, C₂₋₁₂ alkenyl, or C₂₋₁₂heteroalkenyl, each of which is optionally substituted one or more timesby substituents selected independently from R¹⁵; and

R¹⁵ is a halogen atom, —OH, —NH₂, C₁₋₆ alkyl, C₁₋₆ heteroalkyl, C₂₋₆alkenyl, C₂₋₆ heteroalkenyl, C₃₋₁₀ cyclokalkyl, or C₂₋₁₀heterocycloalkyl.

In some such embodiments, X² is C₃₋₁₈ alkylene, C₃₋₁₈ alkenylene, orC₂₋₁₈ oxyalkylene, each of which is optionally substituted one or moretimes by substituents selected from the group consisting of a halogenatom, —OH, —O(C₁₋₆ alkyl), —NH₂, —NH(C₁₋₆ alkyl), and N(C₁₋₆ alkyl)₂. Insome further such embodiments, X² is C₃₋₁₈ alkylene, C₃₋₁₈ alkenylene,or C₂₋₁₈ oxyalkylene, each of which is optionally substituted one ormore times by —OH. In some even further such embodiments, X² is—(CH₂)₂—CH═, —(CH₂)₃—CH═, —(CH₂)₄—CH═, —(CH₂)₅—CH═, —(CH₂)₆—CH═,—(CH₂)₇—CH═, —(CH₂)₈—CH═, —(CH₂)₉—CH═, —(CH₂)₁₀—CH═, —(CH₂)₁₁—CH═,—(CH₂)₁₂—CH═, —(CH₂)₁₃—CH═, —(CH₂)₁₄—CH═, or —(CH₂)₁₅—CH═. In some suchembodiments, X² is —(CH₂)₇—CH═.

In some such embodiments, R¹³ is C₁₋₈ alkyl, C₂₋₈ alkenyl, or C₁₋₈oxyalkyl, each of which is optionally substituted one or more times by—OH. In some further such embodiments, R¹³ is methyl, ethyl, propyl,isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, tert-pentyl,neopentyl, hexyl, or 2-ethylhexyl. In some even further suchembodiments, RB is methyl.

In some such embodiments, R¹⁴ is C₁₋₈ alkyl, C₂₋₈ alkenyl, or C₁₋₈oxyalkyl, each of which is optionally substituted one or more times by—OH. In some further such embodiments, R¹⁴ is methyl, ethyl, propyl,butyl, pentyl, hexyl, heptyl, octyl, or nonyl. In some even further suchembodiments, R¹⁴ is methyl or ethyl. In some embodiments, R¹⁴ is ethyl.

In some embodiments, the internal olefin esters are different compounds.In some other embodiments, however, the internal olefin esters are thesame compound. In some embodiments, the internal olefins esters are bothesters of 9-dodecenoic acid, for example, in some further embodiments,both internal olefin esters are 9-dodecenoic acid methyl ester. In someother embodiments, the internal olefins esters are both esters of9-undecenoic acid, for example, in some further embodiments, bothinternal olefin esters are 9-undecenoic acid methyl ester.

When the internal olefin esters react, an olefinic byproduct (e.g., analkene) is also produced. In some embodiments, where the internal olefinesters react to form an unsaturated dibasic ester, the resulting alkeneis an internal alkene. The identity of the formed internal alkenes willvary depending on the identity of the reacting internal olefin esters.In some embodiments, the resulting internal olefin ester is 2-butene,2-pentene, 2-hexene, 3-hexene, 3-heptene, 4-octene, and the like. Insome embodiments, the resulting internal olefin is 2-butene. In someother embodiments, the resulting internal olefin is 3-hexene. The formedinternal alkene can be vented from the reactor during the course of thereaction, or can be allowed to stay in the reactor. As noted above,metathesis reactions that generate the desired unsaturated dibasicesters can be referred to as “productive metathesis,” as the catalyst isused to make the desired product. In some instances, however, twointernal olefin esters can react in a way that simply generates two newinternal olefin esters. Such metathesis reactions can be referred to as“unproductive metathesis,” as the catalyst is used to make productsbesides the desired unsaturated dibasic esters.

In some other embodiments, the first olefin ester is a terminal olefinester and the second olefin is an internal olefin ester. In some suchembodiments, the terminal olefin ester is a compound of formula (V), asdisclosed above, including all further embodiments thereof. In some suchembodiments, the internal olefin ester is a compound of formula (VI), asdisclosed above, including all further embodiments thereof. In some suchembodiments, the terminal olefin ester is an ester of 9-decenoid acid,such as 9-decenoic acid methyl ester. In some such embodiments, theinternal olefin ester is an ester of 9-undecenoic acid or an ester of9-dodecenoic acid, such as 9-undecenoic acid methyl ester or9-dodecenoic acid methyl ester, respectively.

When the terminal olefin ester reacts with the internal olefin ester, anolefinic byproduct (e.g., an alkene) is also produced. In someembodiments, where the terminal olefin ester and the internal olefinester react to form an unsaturated dibasic ester, the resulting alkeneis a terminal alkene. The identity of the formed internal alkenes willvary depending on the identity of the reacting internal olefin ester. Insome embodiments, the resulting terminal olefin ester is propene,1-butene, 1-pentene, 1-hexene, and the like. In some embodiments, theresulting internal olefin is propene. In some other embodiments, theresulting internal olefin is 1-butene. The formed terminal alkene can bevented from the reactor during the course of the reaction, or can beallowed to stay in the reactor. As noted above, metathesis reactionsthat generate the desired unsaturated dibasic esters can be referred toas “productive metathesis,” as the catalyst is used to make the desiredproduct. In some instances, however, terminal and internal olefin esterscan react in a way that simply generates a terminal olefin ester and aninternal olefin ester. Such metathesis reactions can be referred to as“unproductive metathesis,” as the catalyst is used to make productsbesides the desired unsaturated dibasic esters.

The embodiments above describe different ways in which metathesisreactions can be used to make an unsaturated dibasic ester. In someinstances, however, two or more different productive metathesisreactions may be occurring at the same time. For example, in embodimentswhere the first olefin ester is a terminal olefin ester and the secondolefin ester is an internal olefin ester, the terminal olefin ester andthe internal olefin ester may each react with other molecules of thesame compound, such that two self-metathesis reactions may compete withthe cross-metathesis reaction. Also, in some embodiments, the terminalolefin ester can be generated from the internal olefin ester, e.g., byreacting the internal olefin ester with a terminal alkene in thepresence of a metathesis catalyst. Or, in some alternative embodiments,the internal olefin ester can be generated from the terminal olefinester, e.g., by reacting the terminal olefin ester with an internalalkene in the presence of a metathesis catalyst. In instances where thecross-metathesis reaction of the terminal olefin ester and the internalolefin ester can be kinetically favored, and where only a single olefinester may be available, it can be advantageous to use such processes togenerate different olefin esters, so as to allow for cross-metathesis tooccur at the expense of self-metathesis.

The method includes hydrogenating the unsaturated dibasic ester togenerate a saturated dibasic ester. The hydrogenation can be carried byany suitable means. In certain embodiments, hydrogen gas is reacted withthe unsaturated dibasic ester in the presence of a hydrogenationcatalyst to form a saturated dibasic acid, for example, in ahydrogenation reactor.

Any suitable hydrogenation catalyst can be used. In some embodiments,the hydrogenation catalyst comprises nickel, copper, palladium,platinum, molybdenum, iron, ruthenium, osmium, rhodium, or iridium,individually or in any combinations thereof. Such catalysts may beheterogeneous or homogeneous. In some embodiments, the catalysts aresupported nickel or sponge nickel type catalysts. In some embodiments,the hydrogenation catalyst comprises nickel that has been chemicallyreduced with hydrogen to an active state (i.e., reduced nickel) providedon a support. The support may comprise porous silica (e.g., kieselguhr,infusorial, diatomaceous, or siliceous earth) or alumina. The catalystsare characterized by a high nickel surface area per gram of nickel.Commercial examples of supported nickel hydrogenation catalysts includethose available under the trade designations NYSOFACT, NYSOSEL, and NI5248 D (from BASF Catalysts LLC, Iselin, N.J.). Additional supportednickel hydrogenation catalysts include those commercially availableunder the trade designations PRICAT Ni 62/15 P, PRICAT Ni 55/5, PPRICAT9910, PRICAT 9920, PRICAT 9908, PRICAT 9936 (from Johnson MattheyCatalysts, Ward Hill, Mass.).

The supported nickel catalysts may be of the type described in U.S. Pat.No. 3,351,566, U.S. Pat. No. 6,846,772, European Patent Publication No.0168091, and European Patent Publication No. 0167201, each of which areincorporated by reference herein in their entireties. Hydrogenation maybe carried out in a batch or in a continuous process and may be partialhydrogenation or complete hydrogenation. In certain embodiments, thetemperature ranges from about 50° C. to about 350° C., about 100° C. toabout 300° C., about 150° C. to about 250° C., or about 100° C. to about150° C. The desired temperature may vary, for example, with hydrogen gaspressure. Typically, a higher gas pressure will require a lowertemperature. Hydrogen gas is pumped into the reaction vessel to achievea desired pressure of H₂ gas. In certain embodiments, the H₂ gaspressure ranges from about 15 psig (1 barg) to about 3000 psig (204.1barg), about 15 psig (1 barg) to about 90 psig (6.1 barg), or about 100psig (6.8 barg) to about 500 psig (34 barg). As the gas pressureincreases, more specialized high-pressure processing equipment may berequired. In certain embodiments, the reaction conditions are “mild,”wherein the temperature is approximately between approximately 50° C.and approximately 100° C. and the H₂ gas pressure is less thanapproximately 100 psig. In other embodiments, the temperature is betweenabout 100° C. and about 150° C., and the pressure is between about 100psig (6.8 barg) and about 500 psig (34 barg). When the desired degree ofhydrogenation is reached, the reaction mass is cooled to the desiredfiltration temperature.

The amount of hydrogenation catalyst is typically selected in view of anumber of factors including, for example, the type of hydrogenationcatalyst used, the amount of hydrogenation catalyst used, the degree ofunsaturation in the material to be hydrogenated, the desired rate ofhydrogenation, the desired degree of hydrogenation (e.g., as measure byiodine value (IV)), the purity of the reagent, and the H₂ gas pressure.In some embodiments, the hydrogenation catalyst is used in an amount ofabout 10 percent by weight or less, for example, about 5 percent byweight or less or about 1 percent by weight or less.

Following the metathesis (described above) the resulting composition cancontain various impurities. These impurities can be compounds that weremade by various kinds of unproductive metathesis. Or, in some instances,the impurities may result from the presence of impurities in thestarting compositions. In any event, it can, in some embodiments, bedesirable to strip out and/or distill out these impurities. In some suchembodiments, the stripping and/or distilling can occur after themetathesis, but before the hydrogenation. In some alternativeembodiments, the stripping and/or distilling can occur after both themetathesis and the hydrogenation. These impurities may contain moreesters than hydrocarbons (e.g., monobasic esters), as certain alkeneimpurities can be vented out of the reactor during the metathesisreaction, e.g., due to the lower relative boiling point of the alkeneimpurities. Of course, in some instances, these alkene impurities maystay in the reactor long enough to involve themselves in certainmetathesis reactions, thereby generating other impurities (e.g., anadditional alkene impurity and an additional ester impurity). Paraffinimpurities can also be present, which can be removed by the strippingand/or distilling, for example, after hydrogenation.

In some embodiments, the stripping may lead to the removal of certainamounts of the first olefin ester and/or the second olefin ester. Insome such embodiments, these stripped out reactants can be collected andreused for further metathesis reactions.

In some embodiments, it may be desirable to further purify the saturateddibasic ester prior to the converting. For example, in some embodiments,the saturated dibasic ester can be recrystallized. The recrystallizationcan be carried out by any suitable technique. In general, the dissolvedin a solvent system, for example, with heating, followed by coolinguntil solid crystals of the saturated dibasic ester appear. This can bea suitable means of removing impurities that are more soluble in thesolvent system than the saturated dibasic ester, e.g., shorter-chainmonobasic and dibasic esters and/or acids.

The method includes converting the saturated dibasic ester to asaturated dibasic acid. The concerting can be carried out by anysuitable means. In some embodiments, the saturated dibasic ester ishydrolyzed according to any of the embodiments described above. In someother embodiments, the saturated dibasic ester is converted to asaturated dibasic acid by saponification, followed by acidification.

The resulting saturated dibasic acid can be a dibasic acid according toany of the above embodiments. In some embodiments, the dibasic acid is acompound having the formula: H—OOC—Y—COO—H, wherein Y denotes anyorganic compound (such as hydrocarbyl or silyl groups), including thosebearing heteroatom containing substituent groups. In some suchembodiments, Y is a divalent hydrocarbyl group, which can be optionallysubstituted with various heteroatom-containing substituents, or whosecarbon atoms can be replaced by one or more heteroatoms. Such divalenthydrocarbyl groups can include substituted and unsubstituted alkylene,alkenylene, and oxyalkylene groups.

In some embodiments, the dibasic acid is a compound of formula (II):

wherein,

Y¹ is C₆₋₃₆alkylene or C₆₋₃₆ heteroalkylene, each of which is optionallysubstituted one or more times by substituents selected independentlyfrom R³; and

R³ is a halogen atom, —OH, —NH₂, C₁₋₆alkyl, C₁₋₆ heteroalkyl, C₂₋₆alkenyl, C₂₋₆ heteroalkenyl, C₃₋₁₀ cyclokalkyl, or C₂₋₁₀heterocycloalkyl.

In some embodiments, Y¹ is C₆₋₃₆alkylene or C₄₋₃₆ oxyalkylene, each ofwhich is optionally substituted one or more times by substituentsselected from the group consisting of a halogen atom, —OH,—O(C₁₋₆alkyl), —NH₂, —NH(C₁₋₆alkyl), and N(C₁₋₆alkyl)₂. In some furthersuch embodiments, Y¹ is C₆₋₃₆alkylene, C₆₋₃₆alkenylene, or C₄₋₃₆oxyalkylene, each of which is optionally substituted one or more timesby —OH. In some further such embodiments, Y¹ is —(CH₂)₈—, —(CH₂)₉—,—(CH₂)₁₀—, —(CH₂)₁₁ ^(˜), —(CH₂)₁₂—, —(CH₂)₁₃—, —(CH₂)₁₄—, —(CH₂)₁₅—,—(CH₂)₁₆—, —(CH₂)₁₇—, —(CH₂)₁₈—, —(CH₂)₁₉—, —(CH₂)₂₀—, —(CH₂)₂₁—, or—(CH₂)₂₂—. In some embodiments, Y¹ is —(CH₂)₉—. In some embodiments, Y¹is —(CH₂)₁₂—. In some embodiments, Y¹ is —(CH₂)₁₆—.

In some embodiments, the saturated dibasic acid is undecanedioic acid.In some embodiments, the dibasic ester is tetradecanedioic acid. In someembodiments, the dibasic ester is octadecanedioic acid.

In some embodiments, the saturated dibasic acid can be further purified.In some embodiments, the purification is carried out using therecrystallization methods described above.

FIG. 4 shows an illustrative embodiment for forming a dibasic acid. Themethod 400 includes: reacting a first olefin ester with a second olefinester 401 in the presence of a metathesis catalyst to form a firstalkene and an unsaturated dibasic ester; hydrogenating the unsaturateddibasic ester 402 to form a saturated dibasic ester; and converting thesaturated dibasic ester 403 to form a saturated dibasic acid.

FIG. 5 shows an illustrative embodiment for forming a dibasic acid. Themethod 500 includes: providing a reactant composition comprising a firstolefin ester and a second olefin ester 501; thermally pre-treating thereactant composition 502; reacting the first olefin ester with thesecond olefin ester 503 in the presence of a metathesis catalyst to forman unsaturated dibasic acid; hydrogenating the unsaturated dibasic ester504 to form a saturated dibasic ester (including optional recovery ofthe hydrogenation catalyst, e.g., by filtration); stripping thehydrogenated composition 505 of certain alkene and ester impurities;reacting the saturated dibasic acid with water 506 to form a saturateddibasic acid; decolorizing the hydrolyzed composition 507 (includingrecovery of the decolorizing agent); purifying the saturated dibasicacid (e.g., by recrystallization) 508; drying the solid saturateddibasic acid 509; and packaging of the saturated dibasic acid 510. Insome embodiments, the saturated dibasic acid is octadecanedioic acid. Insome such embodiments, the first and second olefin esters are 9-decenoicacid methyl ester. In some other such embodiments, the first and thesecond olefin esters are both 9-dodecenoic acid methyl ester. In someeven further such embodiments, the first olefin ester is 9-decenoic acidmethyl ester and the second olefin ester is 9-decenoid acid methylester.

FIG. 6 shows an illustrative embodiment for forming a dibasic acid. Themethod 600 includes: providing a reactant composition comprising a firstolefin ester and a second olefin ester 601; thermally pre-treating thereactant composition 602; reacting the first olefin ester with thesecond olefin ester 603 in the presence of a metathesis catalyst to forman unsaturated dibasic acid; hydrogenating the unsaturated dibasic ester604 to form a saturated dibasic ester (including optional recovery ofthe hydrogenation catalyst, e.g., by filtration); stripping thehydrogenated composition 605 of certain alkene and ester impurities;reacting the saturated dibasic acid with water 606 to form a saturateddibasic acid; purifying the saturated dibasic acid (e.g., byrecrystallization) 607; drying the solid saturated dibasic acid 608; andpackaging of the saturated dibasic acid 609. In some embodiments, thesaturated dibasic acid is octadecanedioic acid. In some suchembodiments, the first and second olefin esters are 9-decenoic acidmethyl ester. In some other such embodiments, the first and the secondolefin esters are both 9-dodecenoic acid methyl ester. In some evenfurther such embodiments, the first olefin ester is 9-decenoic acidmethyl ester and the second olefin ester is 9-decenoid acid methylester.

FIG. 7 shows an illustrative embodiment for forming a dibasic acid. Themethod 700 includes: providing a reactant composition comprising a firstolefin ester and a second olefin ester 701; thermally pre-treating thereactant composition 702; reacting the first olefin ester with thesecond olefin ester 703 in the presence of a metathesis catalyst to forman unsaturated dibasic acid; hydrogenating the unsaturated dibasic ester704 to form a saturated dibasic ester (including optional recovery ofthe hydrogenation catalyst, e.g., by filtration); stripping thehydrogenated composition 705 of certain alkene and ester impurities;purifying the saturated dibasic ester, e.g., by recrystallization 706;reacting the saturated dibasic acid with water 707 to form a saturateddibasic acid; decolorizing the hydrolyzed composition 708 (includingrecovery of the decolorizing agent); drying the solid saturated dibasicacid 709; and packaging of the saturated dibasic acid 710. In someembodiments, the saturated dibasic acid is octadecanedioic acid. In somesuch embodiments, the first and second olefin esters are 9-decenoic acidmethyl ester. In some other such embodiments, the first and the secondolefin esters are both 9-dodecenoic acid methyl ester. In some evenfurther such embodiments, the first olefin ester is 9-decenoic acidmethyl ester and the second olefin ester is 9-decenoid acid methylester.

FIG. 8 shows an illustrative embodiment for forming a dibasic acid. Themethod 800 includes: providing a reactant composition comprising a firstolefin ester and a second olefin ester 801; thermally pre-treating thereactant composition 802; reacting the first olefin ester with thesecond olefin ester 803 in the presence of a metathesis catalyst to forman unsaturated dibasic acid; hydrogenating the unsaturated dibasic ester804 to form a saturated dibasic ester (including optional recovery ofthe hydrogenation catalyst, e.g., by filtration); stripping thehydrogenated composition 805 of certain alkene and ester impurities,wherein the stripped impurities include amounts of the first olefinester and the second olefin ester, which are collected and reused insubsequent metathesis reactions 803; reacting the saturated dibasic acidwith water 806 to form a saturated dibasic acid; decolorizing thehydrolyzed composition 807 (including recovery of the decolorizingagent); purifying the saturated dibasic acid (e.g., byrecrystallization) 808; drying the solid saturated dibasic acid 809; andpackaging of the saturated dibasic acid 810. In some embodiments, thesaturated dibasic acid is octadecanedioic acid. In some suchembodiments, the first and second olefin esters are 9-decenoic acidmethyl ester. In some other such embodiments, the first and the secondolefin esters are both 9-dodecenoic acid methyl ester. In some evenfurther such embodiments, the first olefin ester is 9-decenoic acidmethyl ester and the second olefin ester is 9-decenoid acid methylester.

Derivation from Renewable Sources:

The dibasic esters, internal olefin esters, and/or terminal olefinsemployed in any of the above aspects and embodiments can, in certainembodiments, be derived from renewable sources, such as various naturaloils. Any suitable methods can be used to make these compounds from suchrenewable sources. Suitable methods include, but are not limited to,fermentation, conversion by bioorganisms, and conversion by metathesis.

Olefin metathesis provides one possible means to convert certain naturaloil feedstocks into olefins and esters that can be used in a variety ofapplications, or that can be further modified chemically and used in avariety of applications. In some embodiments, a composition (orcomponents of a composition) may be formed from a renewable feedstock,such as a renewable feedstock formed through metathesis reactions ofnatural oils and/or their fatty acid or fatty ester derivatives. Whencompounds containing a carbon-carbon double bond undergo metathesisreactions in the presence of a metathesis catalyst, some or all of theoriginal carbon-carbon double bonds are broken, and new carbon-carbondouble bonds are formed. The products of such metathesis reactionsinclude carbon-carbon double bonds in different locations, which canprovide unsaturated organic compounds having useful chemical properties.

A wide range of natural oils, or derivatives thereof, can be used insuch metathesis reactions. Examples of suitable natural oils include,but are not limited to, vegetable oils, algae oils, fish oils, animalfats, tall oils, derivatives of these oils, combinations of any of theseoils, and the like. Representative non-limiting examples of vegetableoils include rapeseed oil (canola oil), coconut oil, corn oil,cottonseed oil, olive oil, palm oil, peanut oil, safflower oil, sesameoil, soybean oil, sunflower oil, linseed oil, palm kernel oil, tung oil,jatropha oil, mustard seed oil, pennycress oil, camelina oil, hempseedoil, and castor oil. Representative non-limiting examples of animal fatsinclude lard, tallow, poultry fat, yellow grease, and fish oil. Talloils are by-products of wood pulp manufacture. In some embodiments, thenatural oil or natural oil feedstock comprises one or more unsaturatedglycerides (e.g., unsaturated triglycerides). In some such embodiments,the natural oil feedstock comprises at least 50% by weight, or at least60% by weight, or at least 70% by weight, or at least 80% by weight, orat least 90% by weight, or at least 95% by weight, or at least 97% byweight, or at least 99% by weight of one or more unsaturatedtriglycerides, based on the total weight of the natural oil feedstock.

The natural oil may include canola or soybean oil, such as refined,bleached and deodorized soybean oil (i.e., RBD soybean oil). Soybean oiltypically includes about 95 percent by weight (wt %) or greater (e.g.,99 wt % or greater) triglycerides of fatty acids. Major fatty acids inthe polyol esters of soybean oil include but are not limited tosaturated fatty acids such as palmitic acid (hexadecanoic acid) andstearic acid (octadecanoic acid), and unsaturated fatty acids such asoleic acid (9-octadecenoic acid), linoleic acid (9,12-octadecadienoicacid), and linolenic acid (9,12,15-octadecatrienoic acid).

Metathesized natural oils can also be used. Examples of metathesizednatural oils include but are not limited to a metathesized vegetableoil, a metathesized algal oil, a metathesized animal fat, a metathesizedtall oil, a metathesized derivatives of these oils, or mixtures thereof.For example, a metathesized vegetable oil may include metathesizedcanola oil, metathesized rapeseed oil, metathesized coconut oil,metathesized corn oil, metathesized cottonseed oil, metathesized oliveoil, metathesized palm oil, metathesized peanut oil, metathesizedsafflower oil, metathesized sesame oil, metathesized soybean oil,metathesized sunflower oil, metathesized linseed oil, metathesized palmkernel oil, metathesized tung oil, metathesized jatropha oil,metathesized mustard oil, metathesized camelina oil, metathesizedpennycress oil, metathesized castor oil, metathesized derivatives ofthese oils, or mixtures thereof. In another example, the metathesizednatural oil may include a metathesized animal fat, such as metathesizedlard, metathesized tallow, metathesized poultry fat, metathesized fishoil, metathesized derivatives of these oils, or mixtures thereof.

Such natural oils, or derivatives thereof, can contain esters, such astriglycerides, of various unsaturated fatty acids. The identity andconcentration of such fatty acids varies depending on the oil source,and, in some cases, on the variety. In some embodiments, the natural oilcomprises one or more esters of oleic acid, linoleic acid, linolenicacid, or any combination thereof. When such fatty acid esters aremetathesized, new compounds are formed. For example, in embodimentswhere the metathesis uses certain short-chain olefins, e.g., ethylene,propylene, or 1-butene, and where the natural oil includes esters ofoleic acid, an amount of 1-decene, among other products, is formed.Following transesterification, for example, with an alkyl alcohol, anamount of 9-denenoic acid methyl ester is formed. In some suchembodiments, a separation step may occur between the metathesis and thetransesterification, where the alkenes are separated from the esters. Insome other embodiments, transesterification can occur before metathesis,and the metathesis is performed on the transesterified product.

In some embodiments, the natural oil can be subjected to variouspre-treatment processes, which can facilitate their utility for use incertain metathesis reactions. Useful pre-treatment methods are describedin United States Patent Application Publication No. 2011/0113679 andU.S. Provisional Patent Application Nos. 61/783,321 and 61/783,720, bothfiled Mar. 14, 2013, all three of which are hereby incorporated byreference as though fully set forth herein.

In some embodiments, after any optional pre-treatment of the natural oilfeedstock, the natural oil feedstock is reacted in the presence of ametathesis catalyst in a metathesis reactor. In some other embodiments,an unsaturated ester (e.g., an unsaturated glyceride, such as anunsaturated triglyceride) is reacted in the presence of a metathesiscatalyst in a metathesis reactor. These unsaturated esters may be acomponent of a natural oil feedstock, or may be derived from othersources, e.g., from esters generated in earlier-performed metathesisreactions. In certain embodiments, in the presence of a metathesiscatalyst, the natural oil or unsaturated ester can undergo aself-metathesis reaction with itself. In other embodiments, the naturaloil or unsaturated ester undergoes a cross-metathesis reaction with thelow-molecular-weight olefin or mid-weight olefin. The self-metathesisand/or cross-metathesis reactions form a metathesized product whereinthe metathesized product comprises olefins and esters.

In some embodiments, the low-molecular-weight olefin is in the C₂₋₆range. As a non-limiting example, in one embodiment, thelow-molecular-weight olefin may comprise at least one of: ethylene,propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-pentene,3-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene,cyclopentene, 1,4-pentadiene, 1-hexene, 2-hexene, 3-hexene, 4-hexene,2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,2-methyl-2-pentene, 3-methyl-2-pentene, 4-methyl-2-pentene,2-methyl-3-pentene, and cyclohexene. In some instances, ahigher-molecular-weight olefin can also be used.

In some embodiments, the metathesis comprises reacting a natural oilfeedstock (or another unsaturated ester) in the presence of a metathesiscatalyst. In some such embodiments, the metathesis comprises reactingone or more unsaturated glycerides (e.g., unsaturated triglycerides) inthe natural oil feedstock in the presence of a metathesis catalyst. Insome embodiments, the unsaturated glyceride comprises one or more estersof oleic acid, linoleic acid, linoleic acid, or combinations thereof. Insome other embodiments, the unsaturated glyceride is the product of thepartial hydrogenation and/or the metathesis of another unsaturatedglyceride (as described above). In some such embodiments, the metathesisis a cross-metathesis of any of the aforementioned unsaturatedtriglyceride species with another olefin, e.g., an alkene. In some suchembodiments, the alkene used in the cross-metathesis is a lower alkene,such as ethylene, propylene, 1-butene, 2-butene, etc. In someembodiments, the alkene is ethylene. In some other embodiments, thealkene is propylene. In some further embodiments, the alkene is1-butene. And in some even further embodiments, the alkene is 2-butene.

Metathesis reactions can provide a variety of useful products, whenemployed in the methods disclosed herein. For example, terminal olefinsand internal olefins may be derived from a natural oil feedstock, inaddition to other valuable compositions. Moreover, in some embodiments,a number of valuable compositions can be targeted through theself-metathesis reaction of a natural oil feedstock, or thecross-metathesis reaction of the natural oil feedstock with alow-molecular-weight olefin or mid-weight olefin, in the presence of ametathesis catalyst. Such valuable compositions can include fuelcompositions, detergents, surfactants, and other specialty chemicals.Additionally, transesterified products (i.e., the products formed fromtransesterifying an ester in the presence of an alcohol) may also betargeted, non-limiting examples of which include: fatty acid methylesters (“FAMEs”); biodiesel; 9-decenoic acid (“9DA”) esters,9-undecenoic acid (“9UDA”) esters, and/or 9-dodecenoic acid (“9DDA”)esters; 9DA, 9UDA, and/or 9DDA; alkali metal salts and alkaline earthmetal salts of 9DA, 9UDA, and/or 9DDA; dimers of the transesterifiedproducts; and mixtures thereof.

Further, in some embodiments, the methods disclosed herein can employmultiple metathesis reactions. In some embodiments, the multiplemetathesis reactions occur sequentially in the same reactor. Forexample, a glyceride containing linoleic acid can be metathesized with aterminal lower alkene (e.g., ethylene, propylene, 1-butene, and thelike) to form 1,4-decadiene, which can be metathesized a second timewith a terminal lower alkene to form 1,4-pentadiene. In otherembodiments, however, the multiple metathesis reactions are notsequential, such that at least one other step (e.g.,transesterification, hydrogenation, etc.) can be performed between thefirst metathesis step and the following metathesis step. These multiplemetathesis procedures can be used to obtain products that may not bereadily obtainable from a single metathesis reaction using availablestarting materials. For example, in some embodiments, multiplemetathesis can involve self-metathesis followed by cross-metathesis toobtain metathesis dimers, trimmers, and the like. In some otherembodiments, multiple metathesis can be used to obtain olefin and/orester components that have chain lengths that may not be achievable froma single metathesis reaction with a natural oil triglyceride and typicallower alkenes (e.g., ethylene, propylene, 1-butene, 2-butene, and thelike). Such multiple metathesis can be useful in an industrial-scalereactor, where it may be easier to perform multiple metathesis than tomodify the reactor to use a different alkene.

The conditions for such metathesis reactions, and the reactor design,and suitable catalysts are as described above with reference to themetathesis of the olefin esters. That discussion is incorporated byreference as though fully set forth herein.

In the embodiments above, the natural oil (e.g., as a glyceride) ismetathesized, followed by transesterification. In some otherembodiments, transesterification can precede metathesis, such that thefatty acid esters subjected to metathesis are fatty acid esters ofmonohydric alcohols, such as methanol, ethanol, or isopropanol.

FIG. 9 shows a flow chart that illustrates certain embodiments formaking an unsaturated dibasic ester from a feedstock comprising anatural oil. The illustrated method 900 comprises: providing a feedstockcomprising a natural oil 901; reacting the feedstock in the presence ofa metathesis catalyst 902 to form a metathesized product that comprisesesters, e.g., unsaturated glycerides, and olefins; separating (at leasta portion of) the esters from the olefins 903 in the metathesizedproduct; transesterifying the separated esters 904, e.g., in thepresence of an alcohol (e.g., methanol) to form a terminal olefin esterand/or an internal olefin ester; and reacting the internal olefin esterand/or the terminal olefin ester (according to any of the aspects andembodiments described above) 905 to form an unsaturated dibasic ester.The unsaturated dibasic ester can, for example, be further reactedaccording to any of the above aspects and embodiments to form asaturated dibasic acid, such as octadecanedioic acid.

FIG. 10 shows a flow chart that illustrates certain embodiments formaking an unsaturated dibasic ester from a feedstock comprising anatural oil. The illustrated method 1000 comprises: providing afeedstock comprising a natural oil 1001; transesterifying the feedstock1002, e.g., in the presence of an alcohol (e.g., methanol) to form atransesterified product comprising one or more unsaturated fatty acidesters; reacting the unsaturated fatty acid esters 1003, e.g., in thepresence of a metathesis catalyst to form a metathesized productcomprising one or more metathesized unsaturated esters and one or moreolefins; separating (at least a portion of) the metathesized unsaturatedesters from the olefins 1004, e.g., in the metathesized product, whereinthe separated metathesized product comprises a terminal olefin esterand/or an internal olefin ester; and reacting the internal olefin esterand/or the terminal olefin ester (according to any of the aspects andembodiments described above) 1005 to form an unsaturated dibasic ester.The unsaturated dibasic ester can, for example, be further reactedaccording to any of the above aspects and embodiments to form asaturated dibasic acid, such as octadecanedioic acid.

EXAMPLES Examples 1A & 1B—Direct Hydrolysis of 1,18-Octadecanedioic AcidDimethyl Ester (ODDAME)

A 203.4 gram sample of solid ODDAME was charged into a 600 mL HastelloyC Parr reactor vessel equipped with a baffle and two sets of 4×45° pitchblade impellers, internal thermocouple, and sampling dip tube. TheODDAME sample was recrystallized prior to being charged into the vessel.Then, 106.9 grams of deionized water was charged into the reactor. Thereactor vessel was sealed and disposed into the reactor, illustrated inFIG. 2. The reactor included an aluminum block heater, an overhead stirmotor, and a vent line equipped with a pressure regulator that connectsto a condenser. The reactor also has a water feed system.

The reaction mixture was heated to 100° C. to melt the ODDAME (m.p.^(˜)60° C.) under a continuous nitrogen purge (900 sccm) in the reactorheadspace. The pressure regulator on the reactor vent line was adjusteduntil the pressure in the reactor was measured as ^(˜)360 prig. Afterthe regulator was set, the reactor vessel was leak tested at targetedreactor pressure, and the headspace of the system was purged withnitrogen for 30 minutes at 900 sccm. The system was then heated to 225°C. (internal reactor temperature) at 1000 rpm stir rate under a nitrogenpurge headspace of 900 sccm. The condensate receiver was cooled to <15°C. using a glycol chiller system. When the internal reactor reached 223°C., the time was referenced as 0 minutes (e.g., start of the timedreaction). As the reaction proceeded, condensate was retrieved from thecondenser (i.e., condensate receiver) every 30 minutes, and the mass ofthe condensate was measured. Over the ensuing 30 minutes, following thecollection of the condensate, water was charged into the reaction vesselat the time-averaged mass rate of the condensate collected in thecondenser during the previous 30-minute interval (i.e., mass ofcondensate collected in previous 30 minute interval/30 minutes). ForExample 1A, the reaction proceeded for 6 hours at ^(˜)225° C. ForExample 1B, the reaction proceeded for 8 hours at ^(˜)225° C. Then, thewater feed was stopped and the reactor pressure was decreased graduallyto remove water from the reactor. After most of the water was removedfrom the reactor, the reactor contents were transferred under a nitrogenatmosphere to a glass container. Nitrogen headspace maintained untilreactor contents reach at room temperature. The masses of the water andthe reactor contents were measured.

A portion of the sample was analyzed by gas chromatograph (GC). About 1gram of the wet sample was dissolved in toluene (^(˜)10 grams) at95-100° C. Then, 500 μL of the top layer was transferred to a 2 mL GCvial. Then 400 μL of N,O-bis(trimethylsilyl)trifluoroacetamide (AldrichChemical Co., St. Louis, Mo., USA) was added to the GC vial. The vialwas sealed and then heated at 60° C. for 2 hours under agitation (230rpm shaking) until the mixture became homogeneous. Then, the silylatedmaterial was diluted with 300 μL of ethyl acetate. The vial sample wasanalyzed on a GC equipped with an FID detector, a hydrogen carrier gas,and a Restek TG65 capillary column.

Results are reported in Table 1. As used herein, the “Conversion %” is amolar percent and is:100*{[2X_(ODDAME)+X_(ODDA(H)ME)]_(initial)−[2X_(ODDAME)+X_(ODDA(H)ME)]_(final)]}/[2X_(ODDAME)+X_(ODDA(H)ME)]_(initial),where ODDAME refers to 1,18-octadecanedioic acid dimethyl ester,ODDA(H)ME refers to 1,18-octadecanedioic acid monomethyl ester, andX_(ODDAME) and X_(ODDA(H)ME) refer to the mole fraction of ODDAME andODDA(H)ME, respectively. As used herein, “ODDA Yield %” is a molarpercent and is: 100*X_(ODDA)/[X_(ODDA)+X_(ODDAME)+X_(ODDA(H)ME)], whereX_(ODDA) is the mole fraction of ODDA, and the other terms have themeanings as defined above. As used herein, “ODDA(H)ME Yield %” is amolar percent and is:100*X_(ODD(H)ME)/[X_(ODDA)+X_(ODDAME)+X_(ODDA(H)ME)], where the termshave the meanings as defined above. As used herein, the “OverallWater:Oil Molar Ratio” is Z*[(mass of water initially)+(mass of wateradded during reaction)/(mass of water initially), where Z is 10 for a10:1 initial water-to-oil molar ratio, and is 40 for a 40:1 initialwater-to-oil molar ratio.

TABLE 1 Example 1A Example 1B Overall Hydrolysis Reaction 6 8 Time(hours) Initial Water-to-Oil Molar 10 10 Ratio Overall Water:Oil MolarRatio 42.5 80.4 ODDA(H)Me (%, molar) 4.9 0.40 Conversion (%, molar) 97.399.8

Example 1C—Direct Hydrolysis of ODDAME

A 185.0 gram sample of solid ODDAME was charged into a 600 mL HastelloyC Parr reactor vessel equipped with a baffle and two sets of 4×45° pitchblade impellers, internal thermocouple, and sampling dip tube. Then,97.2 grams of deionized water was charged into the reactor. The reactorvessel was sealed and disposed into the reactor, illustrated in FIG. 2.The reactor included an aluminum block heater, an overhead stir motor,and a vent line equipped with a pressure regulator that connects to acondenser. The reactor also has a water feed system.

The reaction mixture was heated to 100° C. to melt the ODDAME (m.p.^(˜)60° C.) under a continuous nitrogen purge (500 sccm) in the reactorheadspace. The pressure regulator on the reactor vent line was adjusteduntil the pressure in the reactor was measured as ^(˜)360 prig. Afterthe regulator was set, the reactor vessel was leak tested at targetedreactor pressure, and the headspace of the system was purged withnitrogen for 30 minutes at 900 sccm. The system was then heated to 225°C. (internal reactor temperature) at 1000 rpm stir rate under a nitrogenpurge headspace of 500 sccm. The condensate receiver was cooled to <15°C. using a glycol chiller system. When the internal reactor reached 223°C., the time was referenced as 0 minutes (e.g., start of the timedreaction). As the reaction proceeded, condensate was retrieved from thecondenser (i.e., condensate receiver) every 30 minutes, and the mass ofthe condensate was measured. Over the ensuing 30 minutes, following thecollection of the condensate, water was charged into the reaction vesselat the time-averaged mass rate of the condensate collected in thecondenser during the previous 30-minute interval (i.e., mass ofcondensate collected in previous 30 minute interval/30 minutes). Thereaction proceeded for 6 hours at ^(˜)225° C. Then, the water feed wasstopped and the reactor pressure was decreased gradually to remove waterfrom the reactor. After most of the water was removed from the reactor,the reactor contents were transferred under a nitrogen atmosphere to aglass container. Nitrogen headspace maintained until reactor contentsreach at room temperature. The masses of the water and the reactorcontents were measured.

A portion of the sample was analyzed by gas chromatograph (GC). About 1gram of the wet sample was dissolved in toluene (^(˜)10 grams) at95-100° C. Then, 500 μL of the top layer was transferred to a 2 mL GCvial. Then 400 μL of N,O-bis(trimethylsilyl)trifluoroacetamide (AldrichChemical Co., St. Louis, Mo., USA) was added to the GC vial. The vialwas sealed and then heated at 60° C. for 2 hours under agitation (230rpm shaking) until the mixture became homogeneous. Then, the silylatedmaterial was diluted with 300 μL of ethyl acetate. The vial sample wasanalyzed on a GC equipped with an FID detector, a hydrogen carrier gas,and a Restek TG65 capillary column. Results are reported in Table 2.

TABLE 2 Example 1C Overall Hydrolysis Reaction 6 Time (hours) InitialWater-to-Oil Molar 10 Ratio Overall Water:Oil Molar Ratio 30.7 ODDA(H)Me(%, molar) 3.4 Conversion (%, molar) 98.3

Example 1D—Direct Hydrolysis of ODDAME

A 203.4 gram sample of solid ODDAME was charged into a 600 mL HastelloyC Parr reactor vessel equipped with a baffle and two sets of 4×45° pitchblade impellers, internal thermocouple, and sampling dip tube. TheODDAME sample was recrystallized prior to being charged into the vessel.Then, 106.9 grams of deionized water was charged into the reactor. Thereactor vessel was sealed and disposed into the reactor, illustrated inFIG. 2. The reactor included an aluminum block heater, an overhead stirmotor, and a vent line equipped with a back-pressure regulator thatconnects to a condenser. The reactor also has a water feed system.

The reaction mixture was heated to 75° C. to melt the ODDAME (m.p.^(˜)60° C.) under a nitrogen in the reactor headspace. Once atemperature of 75° C. was reached, the reactor vessel was leak tested attargeted reactor pressure, and the headspace of the system was purgedwith nitrogen for 30 minutes at 900 sccm. The system was then heated to225° C. (internal reactor temperature) at 1000 rpm stir rate under anitrogen purge headspace of 900 sccm. The condensate receiver was cooledto <15° C. using a glycol chiller system. When the internal reactorreached 223° C., The time was referenced as 0 minutes (e.g., start ofthe timed reaction). The ^(˜)500 sccm headspace nitrogen was sweepthrough the reactor vent line and the vent was adjusted until thepressure in the reactor was measured as ^(˜)300 prig at time zero toremove 135 grams/hour condensate. As the reaction proceeded, condensatewas retrieved from the condenser (i.e., condensate receiver) every 15minutes, and the mass of the condensate was measured. Over the ensuing15 minutes, following the collection of the condensate, water wascharged into the reaction vessel at the time-averaged mass rate of thecondensate collected in the condenser during the previous 15-minuteinterval (i.e., mass of condensate collected in previous 15 minuteinterval/15 minutes). The reaction proceeded for 4 hours at ^(˜)225° C.Then, the water feed was stopped and the reactor pressure was decreasedgradually to remove water from the reactor purge with 250 sccm nitrogenheadspace. After most of the water was removed from the reactor, thereactor contents were transferred under a nitrogen atmosphere to a glasscontainer. Nitrogen headspace maintained until reactor contents reach atroom temperature. The masses of the water and the reactor contents weremeasured. The sample was dried.

About 40 mg of the dry sample was placed into a 2 mL GC vial and add0.40 mL of N,O-bis(trimethylsilyl)trifluoroacetamide (Aldrich ChemicalCo., St. Louis, Mo., USA). The vial was sealed and then heated at 60° C.for 2 hours under agitation (230 rpm shaking) until the mixture becamehomogeneous. Then, the silylated material was diluted with 300 μL ofethyl acetate. The vial sample was analyzed on a GC equipped with an FIDdetector, a hydrogen carrier gas, and a Restek TG65 capillary column.Results are reported in Table 3.

TABLE 3 Example 1D Overall Hydrolysis Reaction 4 Time (hours) InitialWater-to-Oil Molar 10 Ratio Overall Water:Oil Molar Ratio 59.6 ODDA(H)Me(%, molar) 2.9 Conversion (%, molar) 98.2

Comparative Examples 1A & 1B—Direct Hydrolysis of ODDAME

For Comparative Examples 1A and 1B, 90.0 kg sample of solid ODDAME and190 kg of deionized water were charged to a 500 L Hastelloy C pressurereactor (R-0371), equipped with a hot oil jacket. For 1068-69-2, 8.4 kgof solid ODDA (CG400C-121101, from ODDA recovered from 1068-69-1) wasalso charged into the reactor. The reactor lid was secured, and theagitation was started at 100 rpm. The reactor was inerted with nitrogenby pressurizing the reactor with nitrogen to 0.3 MPa, followed byventing to atmospheric pressure for a total of four pressure-ventcycles.

Cycle A:

The reactor temperature was increased to 225° C. over the course of 5 to6 hours. The reactor temperature was held at 225° C. for 4 hours. After4 hours at 225° C., the jacket temperature was cooled 150° C. over thecourse of 2 to 3 hours. At 150° C., the reactor pressure was decreasedto atmospheric pressure and held at atmospheric pressure and 150° C. for5 to 6 hours to evaporate the water and methanol generated from thereaction. The vessel was then recharged with 190 kg of deionized water.Cycle A was repeated an additional 5 times over 5 days. After completionof distillation of methanol and water of the final cycle, the inner tempwas adjusted between 90 and 100° C. Then, 270 kg of toluene was chargedto the reactor and the temperature setpoint was adjusted between 90 and95° C. An azeotropic mixture of toluene and water was distilled awayfrom the ODDA in the 500 L reactor at atmospheric pressure. Thedistillation was stopped when the batch temperature increased from 85 to95° C. Then, 90 kg of azeotropic mixture was removed from the reactorduring the distillation.

Then, another 70 kg of toluene was then recharged to the reactor and thereactor was reheated to between 90 and 95° C. The ODDA and toluene weretransferred under nitrogen into a 500-L mobile tank, which was preheatedto a jacket temperature between 90 and 95° C. A 1000-L glass-linedreactor (R-0322) was preheated to a jacket temperature between 90 and95° C. The ODDA-toluene solution from the 500-L mobile tank wastransferred under nitrogen into the reactor 1000-L glass-lined vessel,and the agitation in the 1000-L vessel was started at 80 rpm. Anadditional 170 kg toluene was charged into the 500 L Hastelloy C reactor(R-0371). The reactor was reheated to between 90 and 95° C. The toluenewas transferred under nitrogen into the 500-L mobile tank, which waspreheated to a jacket temperature between 90 and 95° C. The toluenesolution from the 500-L mobile tank was then transferred under nitrogeninto the reactor 1000-L glass-lined vessel containing the toluene andODDA solution. Then, 6.6 kg of charcoal (GA) was added to the 1000-Lglass-lined vessel containing the ODDA and toluene. The temperature ofthe vessel was reheated to between 90 and 95° C. and held between 90 and95° C. for 2 hours under 80 rpm stirring. After 2 hours, the batch wasfiltered through a Celite bed into a 1000-L stainless steel vessel(R-0321). The filter was preheated with a steam jacket, and the Celitewas preheated by a hot toluene flush, prior to transfer of the batch.

The mixture in the 1000-L stainless steel vessel (R-0321) was slowlycooled to 20±5° C. over the course of 5 to 6 hours under agitation (80rpm). The mixture was then pressure filtered, routing the filtrate tothe 1000-L glass-lined reactor. The filter cake was centrifuged toremove free solvent and to generate a wet cake. The wet cake wasvacuumed dried (ca. −0.086 MPa) in double-cone oven at between 60 and65° C. for 24 hours. The product was collected in polypropylene bags,and the weight and the purity were analyzed. The results of the analysisare shown in Table 4. The results from Examples 1A-1C indicate thepotential to achieve similar conversion and purity using one-third theoverall hydrolysis reaction time while consuming about one-third theamount of water relative to a batch-cycle reaction mode.

TABLE 4 Comparative Comparative Example 1A Example 1B Overall HydrolysisReaction 24 24 Time (hours) Initial Water-to-Oil Molar 40 40 RatioOverall Water:Oil Molar Ratio 240 240 ODDA(H)Me (%, molar) 0.06 0.65Conversion (%, molar) 99.8 99.2

Example 2—Comparison of Color in Samples

Samples prepared according to Examples 1A-1D and Comparative Examples 1Aand 1B were analyzed for the presence of colored impurities. For eachsample, 1 g of the ODDA sample was added to 3 g of dimethylsulfoxide(DMSO). The sample was heated to 60° C. until dissolved. The sample wastransferred to a clear 1-cm-wide cuvette and analyzed for percenttransmittance (% T) of light at wavelengths of 440 nm and 550 nm,respectively. A reference of DMSO was used. The results for each sampleare listed below in Table 5.

TABLE 5 % T at 440 nm % T at 550 nm Example 1A 93.7 96.2 Example 1B 98.799.7 Example 1C 96.7 98.0 Example 1D 93.3 94.1 Comparative 66.8 84.2Example 1A Comparative 45.8 69.1 Example 1B

The percent transmittances of ODDA samples generated according toExamples 1A-1C are higher than the percent transmittances of ODDAgenerated from Comparative Examples 1A and 1B. Therefore, the method ofExamples 1A-1C may obviate the need for additional purification, or mayreduce the amount of additional purification required.

Example 3A—Purification of ODDA

A 150-mL glass filter reactor was charged with 10 g ODDA preparedaccording to Example 1A and 100 mL toluene (Aldrich, 99.8%, anhydrous).The reactor was equipped with a reflux condenser, a thermocouple, and anitrogen blanket. The contents were mechanically stirred using anoverhead agitator, and the reactor jacket was heated to 104° C. Thesolids were dissolved, and the measured internal temperature (solution)was 95° C. The jacket was then cooled at a rate to afford an internaltemperature decrease of about 1° C./minute. Solids appeared at 75.6° C.Cooling was continued at a rate of about 1° C./minute to achieve aninternal temperature of about 50° C. The solution was held at about 50°C. for 15 minutes, and the solids were filtered using a 10-micron filterwith a slight nitrogen pressure. The solids were then washed with 25 mLof fresh toluene and dried under a nitrogen flow for about 2 hours. Thesolids were then removed from the vessel and dried overnight at 80° C.

The dried samples were weighed and the mass was recorded. A portion ofthe sample was derivatized usingN,O-bis(trimethylsilyl)trifluoroacetamide (BTSFA, Aldrich) and analyzedby gas chromatography (gas chromatograph equipped with a FID, hydrogencarrier gas, and a Restek TG65 capillary column). Composition resultsare reported using area and area percent of the chromatogram. Table 6describes the composition of the sample before purification and afterpurification. Table 6 recites the weight percent of ODDA in each sample,the weight percent of dibasic acids (diacids) in each sample, and theweight percent of monobasic acids (monoacids) in each sample.

TABLE 6 Pre-Purification Post-Purification Sample (wt %) Sample (wt %)ODDA Purity 94.6 98.6 Total Diacid Purity 95.4 99.2 Total Monoacid 4.40.8 Impurity

Example 3B—Purification of ODDA

A 150-mL glass filter reactor was charged with 10 g ODDA preparedaccording to Example 1C and 100 mL toluene (Aldrich, 99.8%, anhydrous).The reactor was equipped with a reflux condenser, a thermocouple, and anitrogen blanket. The contents were mechanically stirred using anoverhead agitator, and the reactor jacket was heated to 97° C. Thesolids were dissolved, and the measured internal temperature (solution)was 95.0° C. The jacket was then cooled at a rate of about 1° C./minute(internal solution temperature). Solids appeared at 71.7° C. (internalsolution temperature). Cooling was continued at a rate of about 1°C./minute to achieve an internal temperature of about 50° C. Thesolution was held at about 50° C. for 15 minutes, and the solids werefiltered using a 10-micron filter with a slight nitrogen pressure. Thesolids were then washed with 25 mL of fresh toluene and dried under anitrogen flow for about 2 hours. About 1 g of solids were removed fromthe vessel and dried overnight at 80° C.

The remaining solids were suspended in 100 mL of fresh toluene (Aldrich,anhydrous, 99.8%) in the 150-mL filter reactor. The ODDA was redissolvedin toluene at about 95° C. The jacket was then cooled at a rate of about1° C./minute (internal solution temperature). Solids appeared at 75.5°C. (solution). Cooling was continued at a rate of about 1° C./minute toachieve an internal temperature of about 50° C. The solution was held atabout 50° C. for 15 minutes and the solids were filtered using a10-micron filter with a slight nitrogen pressure. The solids were thenwashed with 25 mL of fresh toluene and dried under nitrogen flow forabout 2 hours. The solids were removed from the vessel and driedovernight at 80° C.

The dried samples were weighed and mass was recorded. A portion of thesample was derivatized using N,O-bis(trimethylsilyl)trifluoroacetamide(BTSFA, Aldrich) and analyzed by gas chromatography (gas chromatographequipped with a FID, hydrogen carrier gas, and a Restek TG65 capillarycolumn). Composition results are reported using area and area percent ofthe chromatogram. Table 7 describes the composition of the sample beforepurification and after purification. Table 7 recites the weight percentof ODDA in each sample, the weight percent of dibasic acids (diacids) ineach sample, and the weight percent of monobasic acids (monoacids) ineach sample.

TABLE 7 Before Sample After First After Second Purification PurificationPurification (wt %) (wt %) (wt %) ODDA Purity 93.1 96.0 98.4 TotalDiacid 94.0 99.0 99.8 Purity Total Monoacid 6.0 1.0 0.2 Impurity

1-25. (canceled)
 26. A method of hydrolyzing a dibasic ester,comprising: introducing a first composition to a reactor, the firstcomposition comprising at least 50 grams of a dibasic ester; andreacting the dibasic ester in the reactor with water to form a secondcomposition comprising a dibasic acid; wherein the second composition issubstantially free of colored impurities.
 27. The method of claim 26,wherein the yield of dibasic acid is at least 75 percent.
 28. The methodof claim 26, wherein the second composition is substantially free ofmonobasic acids.
 29. The method of claim 26, wherein the secondcomposition is substantially free of metal cations.
 30. The method ofclaim 26, wherein the first composition further comprises water.
 31. Themethod of claim 26, wherein the dibasic ester is a compound of formula(I):

wherein, Y¹ is C₆₋₃₆ alkylene, C₆₋₃₆alkenylene, C₆₋₃₆ heteroalkylene, orC₆₋₃₆ heteroalkenylene, each of which is optionally substituted one ormore times by substituents selected independently from R³; R¹ and R² areindependently C₁₋₁₂ alkyl, C₁₋₁₂ heteroalkyl, C₂₋₁₂ alkenyl, or C₂₋₁₂heteroalkenyl, each of which is optionally substituted one or more timesby substituents selected independently from R³; and R³ is a halogenatom, —OH, —NH₂, C₁₋₆ alkyl, C₁₋₆ heteroalkyl, C₂₋₆ alkenyl, C₂₋₆heteroalkenyl, C₃₋₁₀ cyclokalkyl, or C₂₋₁₀ heterocycloalkyl. 32.(canceled)
 33. (canceled)
 34. The method of claim 31, wherein Y¹ is—(CH₂)₈—, —(CH₂)₉—, —(CH₂)₁₀—, —(CH₂)₁₁—, —(CH₂)₁₂—, —(CH₂)₁₃—,—(CH₂)₁₄—, —(CH₂)₁₅—, —(CH₂)₁₆—, —(CH₂)₁₇—, —(CH₂)₁₈—, —(CH₂)₁₉—,—(CH₂)₂₀—, —(CH₂)₂₁—, or —(CH₂)₂₂—.
 35. The method of claim 31, whereinR¹ an R² are independently C₁₋₈ alkyl, C₂₋₈ alkenyl, or C₂₋₈ oxyalkenyl,each of which is optionally substituted one or more times by —OH. 36.The method of claim 35, wherein R¹ and R² are independently methyl,ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl,pentyl, tert-pentyl, neopentyl, hexyl, or 2-ethyl hexyl.
 37. The methodof claim 36, wherein R¹ and R² are methyl.
 38. (canceled)
 39. The methodof claim 26, wherein the reacting is carried out at a reactortemperature of 40° C. to 300° C.
 40. The method of claim 31, wherein thedibasic acid is a compound of formula (II) and the alcohols arecompounds of formula (IIIa) and formula (IIIb):

wherein Y¹, R¹, and R² are as defined in claim
 31. 41. The method ofclaim 26, wherein at least a portion of the formed alcohols are removedfrom the reactor during the reacting.
 42. The method of claim 41,wherein at least 20 percent by weight of the formed alcohols are removedfrom the reactor during the reacting.
 43. The method of claim 26,wherein the formed alcohols are removed continuously orsemi-continuously during the reacting.
 44. The method of claim 26,wherein water is added to the reactor during the reacting.
 45. Themethod of claim 44, wherein the water is added continuously orsemi-continuously during the reacting.
 46. The method of claim 26,wherein the mole-to-mole ratio of water to formed alcohols in thereactor is at least 1:1 during the reacting.
 47. The method of claim 46,wherein the mole-to-mole ratio of water to formed alcohols in thereactor is at least 2:1 during the reacting.
 48. The method of claim 26,wherein the mole-to-mole ratio of the formed dibasic acid to the formedcolored impurities in the second composition is at least 250:1.
 49. Themethod of claim 26, wherein the concentration of O₂ in the reactor doesnot exceed 250 ppm during the reacting, based on the total number ofgaseous species in the reactor. 50-96. (canceled)